• Journal of Microbiology and Biotechnology
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• 제28권8호
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• pp.1346-1351
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• 2018

Oxidoreductases are effective biocatalysts, but their practical use is limited by the need for large quantities of NAD(P)H. In this study, a whole-cell biocatalyst for NAD(P)H cofactor regeneration was developed using the economical substrate glycerol. This cofactor regeneration system employs permeabilized Escherichia coli cells in which the glpD and gldA genes were deleted and the gpsA gene, which encodes $NAD(P)^+-dependent$ glycerol-3-phosphate dehydrogenase, was overexpressed. These manipulations were applied to block a side reaction (i.e., the conversion of glycerol to dihydroxyacetone) and to switch the glpD-encoding enzyme reaction to a gpsA-encoding enzyme reaction that generates both NADH and NADPH. We demonstrated the performance of the cofactor regeneration system using a lactate dehydrogenase reaction as a coupling reaction model. The developed biocatalyst involves an economical substrate, bifunctional regeneration of NAD(P)H, and simple reaction conditions as well as a stable environment for enzymes, and is thus applicable to a variety of oxidoreductase reactions requiring NAD(P)H regeneration.

• Bulletin of the Korean Chemical Society
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• 제24권9호
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• pp.1276-1280
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• 2003

Thermal behavior of bromphenols was investigated by direct pyrolysis at high temperature. The thermal degradation products formed by the pyrolysis of mono-bromophenols (o-, m-, and p-) were identified by gas chromatography-mass spectrometry. During the pyrolysis reactions, several kinds of dioxins and furans were produced, and the relative ratio of pyro-products was dependent on the substituted position of bromine in phenolic structure due to the effect of symmetry and steric hindrance. The formation of dioxins can be explained by the phenoxy radical addition and Br atom elimination at an ortho-carbon site on phenolic structure. On the other hand, the formation of furans can be explained by the ortho-ortho carbon coupling of phenoxy radicals at unsubstituted sites to form o, o'-dihydroxydiphenyl intermediate via its keto-tautomer, followed by $H_2O$ elimination. The pyrolysis temperature has also a substantial effect on the dimerized products quantities but little effect on the type of pyro-products. Moreover, the formation mechanism of pyro-products was suggested on the basis of products identified.

• Bulletin of the Korean Chemical Society
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• 제30권6호
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• pp.1325-1330
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• 2009

A general method has been developed for the solid phase synthesis of drug-like 7-aryl-benzo[b][1,4]oxazin-3(4H)- one derivatives 6. The method relies on a novel, microwave irradiation promoted cyclization reaction of the BOMBA resin bound, N-substituted-$\alpha$-(2-chloro-4-bromophenoxy)acetamide 3 that takes place via a Smiles rearrangement. The 7-bromobenzo[1,4]oxazine 4, produced in this process is converted to 7-aryloxazin analogs 5 by utilizing Suzuki coupling with various substituted arylboronic acids. Finally, the target 7-aryl-benzo[b][1,4]oxazin-3(4H)-ones 6 are liberated from the resin by treatment with 5% TFA. The progress of the reactions involved in this preparative route can be monitored by using ATR-FTIR spectroscopy on a single bead. The target compounds, obtained by using this five-step sequence, are produced in high yields and purities.

• Bulletin of the Korean Chemical Society
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• 제30권2호
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• pp.327-333
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• 2009

For the Pt-catalyzed nucleophilic addition of enones, Pt complexes were employed in the presence of various phosphine ligands and $H_2\;(or\;Et_3SiH),$ affording inter- and intra-molecular coupling products in good to modest yield. Depending on reaction protocols, different phosphine ligands were required to optimize the conditions. In the aldol reaction, the Pt catalyst involving $P(2,4,6-(OMe)_3C_6H_2)3\;or\;P(p-OMeC_6H_4)_3$ was chosen. Michael reaction proceeds in good yields in the presence of $P(p-CF_3C_6H_4)_3$. Regarding the activity of the reductants, $H_2$ exhibited superior activity to $Et_3SiH$, resulting in a shorter reaction time and higher yield in the aldol and Michael reaction. In light of the deuterium labeling studies, the catalytic cycle including the hydrometalation of the enones by the platinum hydride species was proposed.

• Bulletin of the Korean Chemical Society
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• 제30권2호
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• pp.309-314
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• 2009

New poly(arylene-ethynylene)s with silicon-containing ferrocene moiety in the polymer main chain were synthesized via the C-C bond forming reactions of 1,1´-bis(ethynyldimethylsilyl)ferrocene and various aromatic dihalides in high yields. The aromatic dihalides include 1,4-dibromobenzene, 4,4´-dibromobiphenyl, 9,10-dibromoanthracene, 2,5-dibromopyridine, 2,5-dibromothiophene, and 2,6-diiodo-4-nitroaniline. The polymer structures and properties were characterized by such instrumental methods as NMR $(^1H-,\;^{13}C-,\;and\;^{29}Si-)$, IR, UV-visible spectroscopies and TGA/DSC. The spectral data indicated that the present polymers have the regular alternating structure of 1,1´-bis(ethynyldimethylsilyl)ferrocenylene and arylene units. The resulting polymers were completely soluble in such organic solvents as methylene chloride, chloroform, benzene, chlorobenzene, and THF. The thermal behaviors of the resulting polymers were examined.

• ETRI Journal
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• 제26권1호
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• pp.38-44
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• 2004

Searching for systems of self-assembled monolayers (SAMs) that can be used as templates for chemical lithography, we found that nitro groups on aromatic SAMs are selectively converted on Ag to amino groups by irradiation with a visible laser. 4-nitrobenzenethiol on Ag was thus converted to 4-aminobenzenethiol by irradiating it with an $Ar^+$ laser. This was evident from surface-enhanced Raman scattering (SERS) as well as from a coupling reaction forming amide bonds. The surface-induced photoreaction allowed us to prepare patterned binary monolayers on Ag that showed different chemical reactivities. Using the binary monolayers as a lithographic template, we induced site-specific chemical reactions, such as the selective growth of biominerals on either the nitro- or amine-terminated regions by adjusting the crystal-growth conditions. We also demonstrated that patterned, amine-terminated monolayers can be fabricated even on gold by using silver nanoparticles as photoreducing catalysts.

• 한국광물학회지
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• 제23권2호
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• pp.161-170
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• 2010

많은 미생물들이 수용성 망간이온($Mn^{2+}$)을 불용성인 산화망간($Mn^{4+}$) 광물로 산화 침전시키는데, 이와 같은 생물학적 산화반응은 비생물학적 산화반응보다 훨씬 빠르게 일어난다. 이처럼 미생물에 의해 생성된 바이오 산화망간 광물은 표면의 강한 흡착성과 산화환원 반응을 통해 생지구화학 순환과 환경오염물질의 생물흡수도에 큰 역할을 한다. 본 논평은 양자역학의 밀도범함수 이론에 바탕을 둔 전산모사를 이용하여 산화망간 광물 표면의 독성금속 흡착의 자세한 기작과 망간원자 빈자리의 광화학적 역할을 새롭게 밝힌 최근 연구결과를 소개한다.

• 한국전기전자재료학회논문지
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• 제19권6호
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• pp.568-573
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• 2006

We have synthesized new blue light emitting random copolymers, poly(9,9'-n-dioctylfluorene-co-perfluorobenzene-1,4-diyl)s (PFFBs), via Ni(0)-mediated coupling reactions. The weight-average molecular weights ($M_w$) of the PFFB copolymers ranged from 9,000 to 15,000. The PFFB copolymers dissolved in common organic solvents such as THF and toluene. The PL emission peaks of the PFFB copolymers were at around 420, 440, and 470 nm. EL devices were fabricated in ITO/PEDOT/polymer/Ca/Al configurations using these polymers. These EL devices were found to exhibit pure blue emission with approximate CIE coordinates of (0.15, 0.11) at $100cd/m^2$. The blue emissions of these devices might be due to the restriction of the polymer chains to aggregation by introducing of the highly electronegative fluorine moieties. The maximum brightnesses of the PFFB copolymer devices ranged from 140 to $3600cd/m^2$ with maximum efficiencies from 0.2 to 0.6 cd/A. The enhanced efficiency of the PFFB (8/2) copolymer device results from the inhibition of excimer formation by the introduction of the electronegative fluorine moieties into the copolymers.

• 대한화학회지
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• 제43권1호
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• pp.28-42
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• 1999

크기가 큰 치환기의 폴리실란-[2-($R^1R^2$-phenyl)propyl]Si[$R^3$]-[예:$R^1=R^2$=H, $R^3$=n-hexyl; 폴리(2-페닐프로필)(n-헥실)실란]을 초음파 화학적 방법을 사용하여 Wurtz 축합반응에 의해 합성하였다. 초음파는 톨루엔 용매 중 금속 나트륨을 분산시켜 작은 크기와 높은 표면 활성의 나트륨을 형성하였으며 이에 의해 Wurtz 축합반응이 진행되었고 또한 초음파는 부 생성물인 염화나트륨이 나트륨 표면에 침착되는 것을 방지하여 표면활성이 지속적으로 유지되도록 하여 효율적인 반응이 기대되었다. 폴리실란 생성물은 저분자량의 중합체(분자량~$10^3$)와 고분자량의 중합체(분자량~$10^6$)의 혼합물로 얻어 졌다. 전체 수득률은 75-99% 이었으나 $R^3$가 n-hexyl기인 경우에는 혼합비율은 고분자량 중합체가 주 생성물로, cyclohexyl 또는 2-phenylethyl기인 경우에는 저분자량 중합체가 주 생성물로 얻어져 폴리실란의 치환기 종류에 영향을 받는 것으로 나타났으나 $R^1, R^2$의 변화는 영향을 나타내지 않았다.

• 폴리머
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• 제36권5호
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• pp.668-676
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• 2012

본 연구에서는 실리카 나노입자를 bis[3-(trimethoxysilyl)propyl]amine(BTMA) 실란 커플링제로 표면 개질한 후, 실리카에 도입되는 2차 아미노기인 -NH기와 Michael 부가반응이 가능한 acrylate기를 가지는 trimethylolpropane ethoxylate triacrylate(TMPET)와 3-(acryloyloxy)-2-hydroxypropyl methacrylate(AHM)로 표면 처리를 하여 반응성(meth)acrylate기를 가지는 brush를 도입하는 연구를 수행하였다. 1분자에 Michael 부가반응성이 있는 acrylate기를 3개 갖는 TMPET와 1분자에 반응성이 있는 acrylate기와 반응성이 없는 methacrylate기를 각각 1개씩 갖는 AHM을 사용하여, 처리 몰(mol)수의 변화가 실리카 표면에 도입되는 (meth)acrylate기에 미치는 영향을 Fourier transform infrared spectroscopy(FTIR), elemental analysis(EA) 및 고체 상태 cross-polarization magic angle spinning(CP/MAS) nuclear magnetic resonance spectroscopy(NMR)법을 사용하여 분석하였다. BTMA로 개질된 실리카를 TMPET로 처리하면, 액체상태의 순수 TMPET와 순수 BTMA의 반응과는 달리 TMPET 1분자당 3개씩 결합있는 acrylate기 대부분이 BTMA의 -NH기와 Michael 부가반응이 일어나는 것을 확인하였다. 따라서 BTMA로 처리한 실리카에 Michael 부가반응으로 반응성 (meth)acrylate기를 도입하기 위하여서는 AHM과 같이 Michael 부가반응성이 있는 acrylate기와 Michael 부가반응성이 없는 methacrylate기를 각각 1개씩 가지는 AHM을 사용하는 것이 필요함을 확인하였다.