• Journal of the Korean Institute of Electrical and Electronic Material Engineers
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• v.20 no.1
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• pp.80-85
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• 2007

We report the electro-optical properties of the sensory rhodopsin II using a near-field scanning microwave microscope(NSMM). Rhodopsin was known as a photoreceptor pigment with a retinal as a chromophore via a protonated Schiff base and consists of seven ${\alpha}-helical$ transmembrane segments. The sensory rhodopsin II, expressing E. coli UT5600 with endogenous retinal biosynthesis system and purified with $Ni^{-2}-NTA$ affinity chromatography in the presence of 0.02 % DM (Dodecyl Maltoside) from Natronomonas pharaonis. We measured the absorption spectra and the transients difference of sensory rhodopsin II from Natronomonas pharaonis using a UV/VIS spectrophotometer with Nd-Yag Laser (532 nm). The absorption spectra of NpSR II showed a typical rhodopsin spectrum with a left shoulder region and the photointermediates spectra of NpSR II-ground state (${\lambda}max=498\;nm$), NpSR II-M state (${\lambda}max=390\;nm$), and NpSR II-O state (${\lambda}max=550\;nm$) during the photocycle. The observed photocycle reaction was confirmed by measuring the microwave reflection coefficient $S_{11}$ at an operating frequency of f=3.93-3.95 GHz and compared with the results of a photocycle of NpSR II.

• Journal of Photoscience
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• v.1 no.1
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• pp.31-37
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• 1994

Photoirradiation at > 300 nm onto a suspension of platinized TiO$_2$ (TiO$_2$-Pt) particles in an aqueous solution. of N$_{\varepsilon}$-carbamyI-L-lysine (Lys(CONH)$_2$) induced the selective N-cyclization of Lys(CONH$_2$) into almost optically pure L-pipecolinic acid (PCA) under argon atmosphere at ambient temperature. Among various TiO$_2$-Pt catalysts, a P-25 (Degussa) powder platinized via impregnation from chloroplatinic acid followed by hydrogen reduction at 753 K exhibited the highest photocatalytic activity for Lys(CONH$_2$) consumption and L-PCA production. GC-MS analyses of L-PCA obtained photocatalytically from $^{15}$N$\alpha$-Lys(CONH$_2$) revealed the selective formation $^{15}$N-substituted L-PCA. This implies that the mechanism for L-PCA production contains selective cleavage of C$_{\varepsilon}$-N bond and intramolecular alkylation at $\alpha$-amino group. Effect of pH on the rate of this photocatalytic reaction was investigated in detail and compared with the pH-dependent charge distribution in Lys(CONH$_2$) molecule. It is clarified that protonation-deprotonation of $\alpha$-amino group gives marked influence on the rate and selectivity of the photocatalytic reaction. On the basis of these results, it is concluded that the selective production of optically pure L-PCA, especially in an acidic suspension of TiO$_2$-Pt, was attributed to the enhanced protonation of $\alpha$-amino group to prevent undesirable oxidation by photogenerated positive holes and blocking of $\varepsilon$-amino group to yield racemic Schiff base intermediate.

• BMB Reports
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• v.29 no.1
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• pp.32-37
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• 1996

The cysteine 43, potentially important in the activity of O-acetylserine sulfhydrylase (OASS) from Salmonella typhimurium, has been changed to serine. This mutant enzyme (C43S) has been studied in order to gain insight into the structural basis for the binding of inhibitor, substrate and product. UV-visible spectra of C43S exhibit the same spectral change in the presence of OAS as that observed with wild type enzyme, indicating C43S will form an ${\alpha}$-aminoacrylate Schiff base intermediate. At pH 6.5, however, the deacetylase activity of C43S is much higher than wild type enzyme indicating that cysteine 43 plays a role in stabilizing the ${\alpha}$-aminoacrylate intermediate. The fluoroscence spectrum of C43S exhibits a ratio of emission at 340 to 502 nm of 16.9, reflecting the lower fluorescence of PLP and indicating that the orientation of cofactor and tryptophan are different from that of the wild type enzyme. The emission spectrum of C43S in the presence of OAS gives two maxima at 340 and 535 nm. The 535 nm emission is attributed to the fluoroscence of the ${\alpha}$-aminoacrylate intermediate. The visible circular dichroic spectrum was similar to wild type enzyme, but the negative effect observed at 530~550 nm and the molar ellipicity values for the mutant are decreased by about 50% compared to wild type enzyme. The circular dichroic and fluoroscence studies suggest binding of the cofactor is less asymmetric in C43S than in the wild type enzyme.

• BMB Reports
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• v.42 no.1
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• pp.47-52
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• 2009

Alanine racemase catalyzes the interconversion of L-alanine and D-alanine and plays a crucial role in spore germination and cell wall biosynthesis. In this study, alanine racemase produced by Bacillus anthracis was expressed and purified as a monomer in Escherichia coli and the importance of lysine 41 in the cofactor binding octapeptide and tyrosine 270 in catalysis was evaluated. The native enzyme exhibited an apparent $K_m$ of 3 mM for L-alanine, and a $V_{max}$ of $295\;{\mu}moles/min/mg$, with the optimum activity occurring at $37^{\circ}C$ and a pH of 8-9. The activity observed in the absence of exogenous pyridoxal 5'-phosphate suggested that the cofactor is bound to the enzyme. Additionally, the UV-visible absorption spectra indicated that the activity was pH independece, of VV-visible absorption spectra suggests that the bound PLP exists as a protonated Schiff's base. Furthermore, the loss of activity observed in the apoenzyme suggested that bound PLP is required for catalysis. Finally, the enzyme followed non-competitive and mixed inhibition kinetics for hydroxylamine and propionate with a $K_i$of $160\;{\mu}M$ and 30 mM, respectively.

• Journal of the Korean Chemical Society
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• v.27 no.2
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• pp.133-141
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• 1983

The kinetics of the acid-catalyzed hydrolysis of a series of 1-aryl-2-pyrrylideneaniline (3) have been studied in 20% MeOH solution using UV spectrophotometer. Substituents in 3 showed a relatively small effect, with hydrolysis facilitated by electron withdrawing group. By obtaing linear plots of $log k_{obs}$ against Hammett ${\sigma}$ constants, it was able to show that substituents had a considerable contribution to the aromaticity of pyrrole compounds. The small positive ${\rho}$ values were consistent with the rate-determining addition of water to the protonated schiff base in the buffer solution of pH 4 to 8, whereas the addition of water to the free imine seemed to be the rate-determining in the solution of acidities greater than pH 8.

• Bulletin of the Korean Chemical Society
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• v.25 no.8
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• pp.1171-1176
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• 2004

Three banana-shaped achiral compounds, 4-chloro-1,3-phenylene bis [4-{4-(undecenyloxy)phenyl imino-methyl} benzoate] derivatives, were synthesized with variation of a substituent (x=H, F, Cl); their antiferro-electric properties are described. The smectic mesophases, including a switchable chiral smectic C(Sm $C^{\ast}$) phase, were characterized by differential scanning calorimetry, polarizing optical microscopy, triangular wave method, and X-ray diffractometry. The presence of vinyl groups at the terminals of linear side wings in the banana-shaped achiral molecules induced a decrease in melting temperature and formation of the switchable Sm $C^{\ast}$ phase in the melt. The smectic phase having a lateral fluorine-substituent at 3-position of the Schiff's base moiety showed antiferroelctric switching, and the value of spontaneous polarization on reversal of an applied electric field was 250 nC/$cm^2$ .

• Bulletin of the Korean Chemical Society
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• v.31 no.10
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• pp.2813-2818
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• 2010

A novel method was developed for the speciation of chromium in natural water samples based on homogeneous liquid-liquid extraction and determination by flame atomic absorption spectrometry (FAAS). In this method, Cr(III) reacts with a new Schiff's base ligand to form the hydrophobic complex, which is subsequently entrapped in the sediment phase, whereas Cr(VI) remained in aqueous phase. The Cr(VI) assay is based on its reduction to Cr(III) by the addition of sodium sulfite to the sample solution. Thus, separation of Cr(III) and Cr(VI) could be realized. Homogeneous liquid-liquid extraction based on the pH-independent phase-separation process was investigated using a ternary solvent system (water-tetrabutylammonium ion ($TBA^+$)-chloroform) for the preconcentration of chromium. The phase separation phenomenon occurred by an ion-pair formation of TBA and perchlorate ion. Then sedimented phase was separated using a $100\;{\mu}L$ micro-syringe and diluted to 1.0 mL with ethanol. The sample was introduced into the flame by conventional aspiration. After the optimization of complexation and extraction conditions such as pH = 9.5, [ligand] = $1.0{\times}10^{-4}\;M$, [$TBA^+$] = $2.0{\times}10^{-2}\;M$, [$CHCl_3$] = $100.0\;{\mu}L$ and [$ClO_4$] = $2.0{\times}10{-2}\;M$, a preconcentration factor (Va/Vs) of 100 was obtained for only 10 mL of the sample. The relative standard deviation was 2.8% (n = 10). The limit of detection was sufficiently low and lie at ppb level. The proposed method was applied for the extraction and determination of chromium in natural water samples with satisfactory results.

• Journal of the Korean Society of Food Science and Nutrition
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• v.23 no.2
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• pp.251-260
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• 1994

Lipophilic brown pigments produced during the fermentation of domestic Meju and Doenjang were fractionated by column and thin -layer chromatography (TLC). Each of the fractions was tested for the antioxidant activity and then characterized by spectroscopic analysis. The lipophilic brown pigments were separated into chloroform -soluble and methanol-soluble parts in which Meju resulted the higher content of chloroform-soluble part than that of methanol-soluble part ; however, Doenjang exhibited the opposite result to that of Meju. More strong antioxidant activity was found in the methanol-soluble part than the chloroform-soluble part. Four and five fractions were separated from chloroform-soluble and methanol-soluble parts respectively. by silicagel TLC. The fraction that exhibited the high antioxidant activity showed a strong absorption at 260nm caused by amino compounds in UV spectrum The other fractions which did not have antioxidant activity absorbed at 240nm by carbonic acid and it ester,. IR spectrum of each fraction commonly showed absorption at 3400cm-1 , 2800cm-1 , 1700cm-1, 1600cm-1, 1400cm-1 , 1300cm-1 and 1100cm-1. Especially , the fraction which had a strong antioxidant activity showed absorption at 2800cm-1, 1400cm-1, 1600cm-1 suggesting that the fraction contain Schiff's base and primary amine structure.

• 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.

• Natural Product Sciences
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• v.27 no.4
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• pp.245-250
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• 2021

The methylglyoxal (MGO) trapping constituents from Malus baccata L. were investigated using incubation of MGO and crude extract under physiological conditions followed by HPLC analysis. The peak areas of MGO trapping compounds decreased, and their chemical structures were identified by HPLC-ESI/MS. Sieboldin was identified as a major active molecule representing MGO-trapping activity of the crude extract. After reaction of sieboldin and MGO, remaining MGO was calculated by microplate assay method using imine (Schiff base) formation of 2,4-dinitrophenylhydrazine (DNPH) and aldehyde group. After 4 h incubation, sieboldin trapped over 43.8% MGO at a concentration of 0.33 mM and showed MGO scavenging activity with an RC₅₀ value of 0.88 mM for the incubation of 30 min under physiological conditions. It was also confirmed that sieboldin inhibited the production of advanced glycation end products (AGE) produced by bovine serum albumins (BSA)/MGO. Additionally, MGO trapping mechanism of sieboldin was more specifically identified by ¹H-, ¹³C-, 2D NMR and, confirm to be attached to the position of C-3' (or 5').