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121.
Yoon SH Moon JH Choi KM Kim MS 《Rapid communications in mass spectrometry : RCM》2006,20(14):2201-2208
A deflection system consisting of four deflectors was designed and used to reduce the interference from post-source decay (PSD) product ions in photodissociation (PD) tandem time-of-flight (TOF) mass spectrometry. For simple protonated peptides generated by matrix-assisted laser desorption/ionization, the presence of PSD product ions at the laser irradiation spot was found to noticeably alter the minor peaks in the PD spectra even though the major ones were hardly affected. Other benefits from the use of the deflection system such as the improvement in the resolving power in PSD tandem mass spectra are discussed. 相似文献
122.
[Structure: see text] Unique core-modified porphyrinoids, such as oxabenziporphyrins, oxapyriporphyrins, and thiapyriporphyrins, bearing exocyclic C-C double bonds at meso-positions, have been synthesized and characterized. The synthesis was accomplished by utilizing typical "3+1"-type condensation. Two different stable tautomeric forms were isolated, and the two tautomeric forms can be interconvertible upon treatment with base. In contrast, only the structure bearing an exocyclic double bond was isolated in the case of oxapyriporphyrin and oxabenziporphyrin. 相似文献
123.
Carboxylate-bridged diiron(II) centers activate dioxygen for the selective oxidation of hydrocarbon substrates in bacterial multicomponent monooxygenases. Synthetic analogues of these systems exist in which substrate fragments tethered to the diiron(II) core through attachment to an N-donor ligand are oxidized by transient species that arise following the introduction of O2 into the system. The present study describes the results of experiments designed to probe mechanistic details of these oxidative N-dealkylation reactions. A series of diiron(II) complexes with ligands N,N-(4-R-Bn)Bnen, where en is ethylenediamine, Bn is benzyl, and R-Bn is benzyl with a para-directing group R = Cl, F, CH3, t-Bu, or OCH3, were prepared. A Hammett plot of the oxygenation product distributions of these complexes, determined by gas chromatographic analysis, reveals a small positive slope of rho = +0.48. Kinetic isotope effect (KIE(intra)) values for oxygenation of [Fe2(mu-O2CAr(Tol))2(O2CAr(Tol))2(N,N-(C6H5CDH)2en)2] and [Fe2(mu-O2CAr(Tol))2(O2CAr(Tol))2(N,N-(C6H5CD2)(C6H5CH2)en)2] are 1.3(1) and 2.2(2) at 23 degrees C, respectively. The positive slope rho and low KIE(intra) values are consistent with a mechanism involving one-electron transfer from the dangling nitrogen atom in N,N-Bn2en to a transient electrophilic diiron intermediate, followed by proton transfer and rearrangement to eliminate benzaldehyde. 相似文献
124.
Bok Lyeon Lee Yoon Hee Lee Il Yoon Jong Hwa Jung Ki-Min Park Shim Sung Lee 《Microchemical Journal》2001,68(2-3)
Extraction and transport behaviors of isomeric oxathia macrocycles (L2, ortho-; L3, meta- and L4, para-isomer) and their structure related open-chain compound (L1) towards Ag(I) picrate have been examined. From the plot of log (DAg(I)/[pic−]) vs. log [L]0 for all of the ionophores were linear with slope near unity, thereby confirming the 1:1:1 complex formations of Ag(I)/ligand/picrate ion to be extracted into the dichloromethane phase. The extractability of an acyclic ionophore was superior to those of the corresponding cyclic ones. In membrane transport experiments, the slow rate of release of Ag(I) from the membrane into the receiving phase seems to be responsible for lower transport efficiency. Upon addition of sodium thiosulfate as a stripping reagent in receiving phase, the efficiency of transport is significantly enhanced in the order of L1 (acyclic)>L2 (ortho-)>L3 (meta-)>L4 (para-) in accordance with those of log Kex values. It is hypothesized that the ion-pair complexation of L1 in extraction step would be more favorable in extraction and transport of Ag(I). Its structure have been confirmed by X-ray diffraction analysis of [Ag(L1)pic], where L1=1,10-bis(mercaptobenzylyl)-4,7-dioxadecane. 相似文献
125.
Jhung SH Yoon JW Lee JS Chang JS 《Chemistry (Weinheim an der Bergstrasse, Germany)》2007,13(22):6502-6507
Several zeolites, such as faujasite, mordenite, and ZSM-5, with various aluminum contents have been used to analyze the effect of aluminum or cation concentration (strength of electrostatic field) on hydrogen adsorption at low temperature. Irrespective of the zeolite structure, the adsorption capacity, isosteric heat of adsorption (-DeltaHads), surface coverage, and micropore occupancy increase with increasing aluminum content of a zeolite. Zeolites with a higher amount of aluminum favorably adsorb hydrogen at relatively low pressures. For zeolites with similar aluminum contents, the adsorption capacity, isosteric heat of adsorption, surface coverage, and micropore occupancy are in the order of mordenite>ZSM-5>faujasite, probably due to differing pore sizes and the presence or absence of pore intersections. This work demonstrates that zeolites with strong electrostatic fields and narrow pores without intersections are beneficial for high hydrogen uptake. 相似文献
126.
The electronic structure of multiwalled carbon nanotubes (CNTs) has been investigated, depending on the growth temperature, using synchrotron X-ray photoelectron spectroscopy (XPS) and field emission measurements. The vertically aligned CNTs are grown via pyrolysis of ferrocene and acetylene in a broad temperature range 600-1000 degrees C. The CNTs have a cylindrical structure with a uniform diameter of 20 nm. As growth temperature increases, due to an improved crystallinity of the graphitic sheets, the width of the XPS C 1s peak becomes narrower and the intensity of the valence band increases. Field emission from the as-grown CNTs exhibits a large enhancement of current density with growth temperature, strongly correlated with the electronic structure revealed by XPS. 相似文献
127.
Gold Nanorod–Photosensitizer Complex Obtained by Layer‐by‐Layer Method for Photodynamic/Photothermal Therapy In Vitro 下载免费PDF全文
Seung Beom Kim Tae Heon Lee Prof. Il Yoon Prof. Young Key Shim Prof. Woo Kyoung Lee 《化学:亚洲杂志》2015,10(3):563-567
Gold nanorod (GNR)–photosensitizer (PS) complex was prepared using anionic PS (sodium salt of purpurin‐18) and cationic poly(allylamine hydrochloride) by layer‐by‐layer method, and was characterized by transmission electron microscopy, UV‐vis spectroscopy, and zeta potential. The GNR–PS complex is a promising agent for synergistic (photothermal and photodynamic) therapy (PTT/PDT), in which PTT generates heat as well as operates the PS release which maximize the following PDT activity. The combined dual therapy, PTT followed by PDT, exhibits a significantly higher photocytotoxicity result based on synergistic effect of hyperthermia from PTT as well as singlet oxygen photogeneration from PDT. 相似文献
128.
Tuning the Redox Properties of a Nonheme Iron(III)–Peroxo Complex Binding Redox‐Inactive Zinc Ions by Water Molecules 下载免费PDF全文
Dr. Yong‐Min Lee Suhee Bang Heejung Yoon Seong Hee Bae Dr. Seungwoo Hong Dr. Kyung‐Bin Cho Dr. Ritimukta Sarangi Prof. Dr. Shunichi Fukuzumi Prof. Dr. Wonwoo Nam 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(30):10676-10680
Redox‐inactive metal ions play important roles in tuning chemical properties of metal–oxygen intermediates. Herein we report the effect of water molecules on the redox properties of a nonheme iron(III)–peroxo complex binding redox‐inactive metal ions. The coordination of two water molecules to a Zn2+ ion in (TMC)FeIII‐(O2)‐Zn(CF3SO3)2 ( 1 ‐Zn2+) decreases the Lewis acidity of the Zn2+ ion, resulting in the decrease of the one‐electron oxidation and reduction potentials of 1 ‐Zn2+. This further changes the reactivities of 1 ‐Zn2+ in oxidation and reduction reactions; no reaction occurred upon addition of an oxidant (e.g., cerium(IV) ammonium nitrate (CAN)) to 1 ‐Zn2+, whereas 1 ‐Zn2+ coordinating two water molecules, (TMC)FeIII‐(O2)‐Zn(CF3SO3)2‐(OH2)2 [ 1 ‐Zn2+‐(OH2)2], releases the O2 unit in the oxidation reaction. In the reduction reactions, 1 ‐Zn2+ was converted to its corresponding iron(IV)–oxo species upon addition of a reductant (e.g., a ferrocene derivative), whereas such a reaction occurred at a much slower rate in the case of 1 ‐Zn2+‐(OH2)2. The present results provide the first biomimetic example showing that water molecules at the active sites of metalloenzymes may participate in tuning the redox properties of metal–oxygen intermediates. 相似文献
129.
Nishat Arshi Junqing Lu Yun Kon Joo Jae Hong Yoon Bon Heun Koo 《Surface and interface analysis : SIA》2015,47(1):154-160
Nanocrystalline tantalum nitride (TaN) thin films have been deposited by reactive direct current magnetron sputtering technique on Si/SiO2 (100) substrate with nitrogen flow rate ranging from 0, 3, 5, 7, 9 to 11 standard cubic centimeter per minute (sccm). Structural properties, surface morphology, chemical composition and and resistivity of the TaN films were investigated by X‐ray diffraction (XRD), field emission scanning electron microscopy, X‐ray photoemission spectroscopy (XPS) and four‐point probe measurements, respectively. In the XRD spectra, a classical formation sequence of tantalum nitride phases in the order of Ta‐Ta2N‐TaN‐Ta4N5 and decreasing amount of metallic Ta were observed with increasing nitrogen flow. The electrical resistivity of the TaN film was found to increase with increasing N/Ta ratio as a result of the increased electron scattering from interstitial N atoms. In the XPS analysis, two groups of Ta4f doublets relating to different TaN phases were observed in the core level spectra of TaN films. No strong coupling was observed between the Ta4f doublets and the Ta4p and the N1s groups. The appropriate nitrogen flow was believed to be helpful in the bonding and formation of stoichiometric TaN. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
130.
Lippow SM Moon TS Basu S Yoon SH Li X Chapman BA Robison K Lipovšek D Prather KL 《Chemistry & biology》2010,17(12):1306-1315
Engineered biosynthetic pathways have the potential to produce high-value molecules from inexpensive feedstocks, but a key limitation is engineering enzymes with high activity and specificity for new reactions. Here, we developed a method for combining structure-based computational protein design with library-based enzyme screening, in which inter-residue correlations favored by the design are encoded into a defined-sequence library. We validated this approach by engineering a glucose 6-oxidase enzyme for use in a proposed pathway to convert D-glucose into D-glucaric acid. The most active variant, identified after only one round of diversification and screening of only 10,000 wells, is approximately 400-fold more active on glucose than is the wild-type enzyme. We anticipate that this strategy will be broadly applicable to the discovery of new enzymes for engineered biological pathways. 相似文献