• Corrosion Science and Technology
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• v.8 no.2
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• pp.81-88
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• 2009

Chloride induced corrosion of steel reinforcement inside concrete is a major concern for concrete structures exposed to a marine environment. It is well known that transport of chloride ions in concrete occurs mainly through ionic/molecular diffusion, as a gradient of chloride concentration in the concrete pore solution is set. In the process of chloride transport, a portion of chlorides are bound in cement matrix then to be removed in the pore solution, and thus only the rest of chlorides which are not bound (i.e. free chlorides) leads the ingress of chlorides. However, since the measurement of free/bound chloride content is much susceptible to environmental conditions, chloride profiles expressed in total chlorides are evaluated to use in many studies In this study, the capacity of chloride binding in cement matrix was monitored for 150 days and then quantified using the Langmuir isotherm to determine the portions of free chlorides and bound chlorides at given total chlorides and the redistribution of free chlorides. Then, the diffusion of chloride ion in concrete was modeled by considering the binding capacity for the prediction of chloride profiles with the redistribution. The predicted chloride profiles were compared to those obtained from conventional model. It was found that the prediction of chloride profiles obtained by the model has shown slower diffusion than those by the conventional ones. This reflects that the prediction by total chloride may overestimate the ingress of chlorides by neglecting the redistribution of free chlorides caused by the binding capacity of cement matrix. From the evaluation, it is also shown that the service life prediction using the free chloride redistribution model needs different expression for the chloride threshold level which is expressed by the total chlorides in the conventional diffusion model.

• Journal of the Korean Chemical Society
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• v.54 no.6
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• pp.671-679
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• 2010

The geometrical parameters and binding energies of the benzene ion-water complex [$C_6H_6^+-(H_2O)_n$(n=1-5)] have been investigated using ab initio (MP2) and density functional theory (DFT) with large basis sets. The harmonic vibrational frequencies and IR intensities are also determined to confirm that all the optimized geometries are true minima. Also zero-point vibrational energies have been considered to predict the binding energies. The predicted binding energy of 8.6 kcal/mol for $C_6H_6^+-(H_2O)$ at the MP2/aug-cc-pVTZ level of theory is in excellent agreement with recent experimental result of $8.5{\pm}1$ kcal/mol.

• Journal of the Korea Institute of Building Construction
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• v.4 no.4
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• pp.95-101
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• 2004

The purpose of this paper is to compare free-chloride content with water-soluble chloride in blast furnace cement(BSC) paste. The content of free-chloride in cement paste measured by pore solution analysis and water-soluble chloride measured by ASTM. The result of this study are as follows: 1. The concentration of chloride ion in pore solution of BSC-solidified matrix is almost as low as 43-71% compared to that of OPC-solidified matrix containing the same chloride content in cement paste. 2. The binding capacity of specimens, OPC Pl-P5, are 93.5-77%, but the binding capacity of specimens, BSC Pl-P5 are 97.1-86.1%, which is to be as high as 2-9.1% compared to OPC containing the same chloride content. 3. In terms of water-soluble chloride content in BSC paste are 15-31.7 percent of chloride addition but free-chloride content in pore solution are 2.9-13.9 percent of chloride addition. The free-chloride content in pore solution is 19.3-43.8 percent lower for the water-soluble chloride content in cement paste.

• Bulletin of the Korean Chemical Society
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• v.27 no.9
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• pp.1445-1449
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• 2006

Molecular tweezers based on chenodeoxycholic acid bearing different lengths of arm were synthesized andtheir anion binding affinities were evaluated by $^1H$ NMR, isothermal calorimetric titration, and ESI mass spectrometry. Molecular tweezer 6 showed a high selectivity toward $H_2PO_4\;^-$ over $Cl^-,\;Br^-,\;I^-, $ and $CH_3CO_2\;^-$ by $^1H$ NMR titration, whereas the association constant for $F^-$ revealed the largest value as determined by ITC. The selectivity of 6 towards $F^-$ was about 103 times higher than that of $Cl^-,\;H_2PO_4\;^- $, and $CH_3CO_2\;^-$. ITCexperiment of 6 with $F^-$ in a DMSO showed two binding modes; two sequential association constants $K_1\;=\;2.77\;{\times}\;10^5\;M^{-1}$ and $K_2\;=\;8.68\;{\times}\;10^6\;M^{-1}$ were found. These sequential bindings were confirmed by ESI massspectrometry. 1 : 1 and 1 : 2 complexes of 6 and $F^-$ were found at m/z 868.08 and 884.04.

• Bulletin of the Korean Chemical Society
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• v.34 no.7
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• pp.1990-1994
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• 2013

A novel multi-cationic borane, tri-N-methylpyridinium substituted triarylborane, $[BAr^N_3]I_3$ ($[2]I_3$) ($Ar^N=4-(4-C_5H_4N-Me)-2,6-Me_2-C_6H_2$) was prepared from the corresponding neutral tris-pyridyl borane, $BAr_3$ (2a) ($Ar=4-(4-C_5H_4N)-2,6-Me_2-C_6H_2$). The crystal structure of 2a determined by X-ray diffraction study reveals the presence of tri-coordinate boron center with peripheral pyridyl moieties. The fluoride ion affinity of the cationic borane, $[2]I_3$ was investigated by UV-vis absorption titrations and was compared with that of neutral 2a. While 2a binds fluoride with the binding constant of $1.9{\times}10^2\;M^{-1}$ in $THF/H_2O$ (9:1 v/v) mixture, $[2]I_3$ shows a very high binding constant ($K=1.0{\times}10^8\;M^{-1}$) that is greater by six orders of magnitude than that of 2a in the same medium. This result indicates that the fluorophilicity of triarylborane can be drastically enhanced by multiple pyridinium substitutions.

• Bulletin of the Korean Chemical Society
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• v.30 no.9
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• pp.2051-2056
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• 2009

The rate constants of alkaline fading of malachite green ($MG^+$) was measured in the presence of nonionic (TX-100), cationic (DTAB) and anionic (SDS) surfactants. This reaction was studied under pseudo-first-order conditions at 283∼303 K. The rate of fading reaction showed noticeable dependence on the electrical charge of the used surfactants. It was observed that the reaction rate constants were increased in the presence of TX-100 and DTAB and decreased in the presence of SDS. According to Hughs-Ingold rules for nucleophilic substitution reactions, the electric charge of MG/surfactant compound along with decrease in dielectric constant of $MG^+$ micro-environment in this compound varies the rate of fading reaction. Binding constants of surfactant molecules to $MG^+$ were calculated using cooperativity, pseudo-phase ion exchange and classical models and the related thermodynamic parameters were obtained by classical model. The results show that the binding of $MG^+$ to TX-100 is exothermic and binding of $MG^+$ to DTAB and SDS in some concentration ranges of the used surfactants is endothermic and in the other ones is exothermic.

• BMB Reports
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• v.30 no.2
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• pp.125-131
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• 1997

This work reports studies of the catalytic and structural properties of pyridoxal kinase (ATP: pyridoxal 5' -phosphotransferase, EC. 2.7.1.35), Pyridoxal kinase catalyzes the phosphorylation of vitamin $B_6$ (pyridoxal, pyridoxamine, pyridoxine) using ATP-Zn as a phosphoryl donor. The enzyme purified from brain tissues is made up of two identical subunits of 40 kDa each. Native enzyme was inhibited by a substrate analogue, pyridoxal-oxime. Limited chymotrypsin digestion of pyridoxal kinase yields two fragments of 24 and 16 kDa with concomitant loss of catalytic activity. These fragments were isolated by DEAE ion exchange chromatography and used for binding studies with fluorescent ATP and pyridoxal analogues. The spectroscopic properties of both fluorescent pyridoxal analogue and Anthraniloyl ATP (Ant-ATP) bound to the 24 kDa fragment are indistinguishable from those of both pyridoxal analogue and Ant-ATP bound to the native pyridoxal kinase, respectively. The small 16 kDa fragment, generated by proteolytic cleavage of the kinase, does not bind any of the substrate analogues. Binding characteristics of Ant-ATP were extensively studied by measuring the changes in fluorescence spectra at various conditions. From the results presented herein, it is postulated that the structural domain associated with catalytic activity comprises approximately one-half of the molecular mass of pyridoxal kinase (24 kDa). whereas the remaining portion (16 kDa) of the enzyme contains a regulatory binding domain.

• Biotechnology and Bioprocess Engineering:BBE
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• v.3 no.2
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• pp.82-86
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• 1998

The maltose binding protein (MBP) fusion protein system is a versatile tool to express and isolate recombinant proteins in E. coli. In this system, MBP fusion proteins are efficiently isolated from whole cell lysate using amylose conjugated agarose beads and then eluted by competition with free maltose. Since MBP is a rather large molecule (∼42 kDa), for further experiments, the MBP part is usually proteolytically cleaved from the fusion protein and subsequently removed by ion-exchange chromatography or rebinding to amylose columns after washing out excess and MBP-bound maltose. In the present study, we have developed an improved method for the removal of cleaved MBP, which is advantageous over conventional methods. In this method, factor Xa cleaved MBP fusion proteins were incubated with Sepharose beads conjugated with MBP specific monoclonal antibodies and then precipitated buy centrifugation, resulting in highly purified proteins in the supernatant.

• Bulletin of the Korean Chemical Society
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• v.25 no.5
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• pp.726-736
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• 2004

In this paper, kinetics of reaction between Bromophenol blue (BPB) and $OH^-$, called fading, has been studied through a spectrophotometric method in the presence of nonionic Triton X-100 (TX-100), anionic sodium dodecyl sulfate (SDS) and cationic dodecyl trimethylammonium bromide (DTAB) surfactants. The influence of changes in the surfactant concentration on the observed rate constant was investigated. The results are treated quantitatively by pseudophase ion-exchange (PPIE) model and a new simple model called "classical model". The binding constants of BPB molecules to the micelles and free molecules of surfactants, their stoichiometric ratios and thermodynamic parameters of binding have been evaluated. It was found that SDS has nearly no effect on the fading rate up to 10 mM, whereas TX-100 and DTAB interact with BPB which reduce the reaction rate. By the use of fading reaction of BPB, the binding constants of SDS molecules to TX-100 micelles and their Langmuir and Freundlich adsorption isotherms were obtained and when mixtures of DTAB and TX-100 were used, no interaction was observed between these two surfactants.

• BMB Reports
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• v.38 no.4
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• pp.407-413
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• 2005

Calcium and zinc binding protein, calprotectin is a multifunctional protein with broad spectrum antimicrobial and antitumoural activity. It was purified from human neutrophil, using a two-step ion exchange chromatography. Since surface hydrophobicity of calprotectin may be important in membrane anchoring, membrane penetration, subunits oligomerization and some biological roles of protein, in this study attempted to explore the effect of calcium in physiological range on the calprotectin lipophilicity. Incubation of human calprotectin ($50\;{\mu}g/ml$) with different calcium concentrations showed that 1-anilino-8-naphthalene sulfonic acid (ANS) fluorescence intensity of the protein significantly elevates with calcium in a dose dependent manner, suggesting an increase in calprotectin surface hydrophobicity upon calcium binding. Our study also indicates that calcium at higher concentrations (6, 8 and 10 mM) induces aggregation of human calprotectin. Our finding demonstrates that the starting time and the rate constant of calprotectin aggregation depend on the calcium concentration.