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981.
Kim H Samsonenko DG Yoon M Yoon JW Hwang YK Chang JS Kim K 《Chemical communications (Cambridge, England)》2008,(39):4697-4699
Microporous manganese formate shows temperature-triggered gate opening for nitrogen and argon adsorption, which is not due to a structural change of the framework but due to dynamic opening of the pore aperture and/or sufficient kinetic energy of the adsorbates to overcome a diffusion barrier above a critical temperature. 相似文献
982.
Myungkoo Suh Prof. Ho‐Jin Lee Jin‐Young Park U‐Hwang Lee Dr. Young‐Uk Kwon Prof. Deug Joong Kim Prof. 《Chemphyschem》2008,9(10):1402-1408
Uptake and release processes of various fluorescent rhodamine dyes and antitumor drugs to/from an ordered mesoporous silica film are investigated by means of UV/Vis absorption and fluorescence spectroscopies. The pores in the 160 nm‐thick silica film strongly withdraw the dyes from water, thus allowing the storage of several micrograms of guest molecules per square centimeter of film. The binding equilibrium of the dyes follows a Langmuir‐type adsorption. The dissociation constant, Kd, and the maximum binding amount to the film, , are determined by fitting the binding curves. The release kinetics of the guests from the film to a simulated body fluid (SBF) solution follows a bimodal first‐order exponential behavior. The release kinetics from the mesoporous thin film is remarkably retarded relative to that from mesoporous powders. Among all the studied dyes, rhodamine 101 is released most slowly, which implies that the release rate depends not only on the interactions between the guests and the silica surface, but also on intermolecular interactions between the guest molecules. Comparison of the release kinetics of different antitumor drugs, such as actinomycin D and mitoxantrone, into an SBF solution shows that mitoxantrone is released much slowly. This slower release is attributed to the positive molecular charge and the formation of dimers in the pores. 相似文献
983.
The first stereoselective total synthesis of the bibenzyl tetrahydrocannabinol, (-)-perrottetinene, has been achieved from readily available starting materials. The absolute stereochemistry is derived from a chiral gamma-hydroxy vinylstannane. The key reaction is the synthesis of the cis-disubstituted cyclohexene ring of perrottetinene by diastereoselective Ireland-Claisen rearrangement and a ring-closing metathesis reaction. The absolute configuration of (-)-perrottetinene is proposed. 相似文献
984.
We calculate and compare the effects of aprotic vs protic solvent on the rate of SN2 reaction [F- + C3H7OMs--> C3H7F + OMs-]. We find that aprotic solvent acetonitrile is more efficient than a small protic solvent such as methanol. Bulky protic solvent (tert-butyl alcohol) is predicted to be quite efficient, giving the rate constant that is similar to that in CH3CN. Our calculated relative activation barriers of the SN2 reaction in methanol, tert-butyl alcohol, and CH3CN are in good agreement with experimental observations. 相似文献
985.
Sung PJ Lin MR Hwang TL Fan TY Su WC Ho CC Fang LS Wang WH 《Chemical & pharmaceutical bulletin》2008,56(7):930-935
Four new briarane-related diterpenoids, designated as briaexcavatins M-P (1-4), were isolated from the cultured octocoral Briareum excavatum. The structures, including the relative configurations of natural products 1-4 were established on the basis of extensive spectral data analysis and by comparison with the spectral data from other known metabolites featuring a briarane carbon skeleton. 相似文献
986.
Yoon SM Hwang IC Shin N Ahn D Lee SJ Lee JY Choi HC 《Langmuir : the ACS journal of surfaces and colloids》2007,23(23):11875-11882
One-dimensional (1D) helical organic nanostructures were synthesized by a modified vapor-solid (VS) process, called the vaporization-condensation-recrystallization (VCR) process. The conventional solution-phase synthetic methods generally mediate self-assemblies of repeating unit molecules. To provide enough intermolecular interaction forces among the unit molecules, such strategy requires specific designs and syntheses of complex unit molecules as they possess numerous functional groups including phenyl rings, hydroxyl groups, long aliphatic chains, etc. On the contrary, we found that small and simple organic molecules, for example, m-ABA, could be self-assembled by the VCR process, resulting in 1D helical organic nanostructures. When m-aminobenzoic acid (m-ABA) powders were vaporized and transported to be condensed on a cooler region, the condensates were recrystallized into 1D helical nanobelts. Each step of the VCR process was confirmed from control experiments performed by varying reaction times, substrate types, and reaction temperatures. Powder XRD data, SAED analysis, and theoretical calculations revealed that dimers of m-ABA molecules have repeating units, and the growth axis of m-ABA nanohelices is [100]. 相似文献
987.
Hwang WL Holden MA White S Bayley H 《Journal of the American Chemical Society》2007,129(38):11854-11864
Aqueous droplets submerged in an oil-lipid mixture become enclosed by a lipid monolayer. The droplets can be connected to form robust networks of droplet interface bilayers (DIBs) with functions such as a biobattery and a light sensor. Such DIB networks might be used as model systems for the study of membrane-based biological phenomena. In this study, we develop and experimentally validate an electrical modeling approach for DIB networks by applying it to describe the current flow through a simple network containing protein pores and blocking molecules. We demonstrate the use of SPICE (Simulation Program with Integrated Circuit Emphasis) for simulating the electrical behavior of DIB networks. The modular and scalable nature of DIB networks should enable a straightforward extension of the analysis presented in this paper to large, complex networks. 相似文献
988.
Yang FA Guo CW Chen YJ Chen JH Wang SS Tung JY Hwang LP Elango S 《Inorganic chemistry》2007,46(2):578-585
The crystal structures of the dimer form of copper(II) tetraphenylporphyrin N-oxide, [Cu(tpp-N-O)]2 (3-dimer), and zinc(II) tetraphenylporphyrin N-oxide, [Zn(tpp-N-O)]2 (4-dimer), were established. The geometry at the copper ion in 3-dimer is essentially square-pyramidal with one oxygen bridge [O(1A)] occupying the apical site, giving a much larger Cu-O bond distance compared to those at the basal plane. The respective Cu...Cu distance and Cu-O-Cu angle in the core of 3-dimer are 3.987(4) A and 148.1(3) degrees. The Zn(1) atom in 4-dimer has a distorted square-pyramidal [4 + 1] coordination geometry that gives a tau-value of 0.19. The respective Zn...Zn distance and Zn-O-Zn angle in the dimeric unit of 4-dimer are 4.025(3) A and 148.1(2) degrees. The 3-dimer displays axial X-band electron paramagnetic resonance spectral features (Es = 0) in the powder state at 4 K, giving g parallel = 2.51 (A(parallel,s) = (9.6 +/- 0.2) x 10-3 cm(-1)) and g(perpendicular) = 2.11 and in the same powder state at 293 K giving Ds = 0.0731 cm(-1) (as derived from DeltaMs = 1 lines) or 0.0743 cm(-1) (as derived from the DeltaMs = 2 lines). In addition, 3-dimer displays a DeltaMs = 2 transition at g = 4.17 indicating the presence of spin-exchange coupling. The anisotropic exchange interaction (Ds(ex)= 0.132 cm(-1)) gives the main contribution to Ds in 3-dimer. The theoretical fit of the susceptibility and effective magnetic moment data of 3-dimer in the temperature range of 5-300 K gives 2J = 68 cm(-1), g = 2.01, p = 0.06, and a temperature-independent paramagnetism of 10(-6) cm3 mol(-1). This magnetic susceptibility data indicates that the copper(II) ions in 3-dimer are coupled in a ferromagnetic manner with the ground-spin triplet stabilized by 68 cm(-1) with regard to the singlet. 相似文献
989.
Double-quantum-filtered NMR and T(1) inversion-recovery spectroscopy were employed to exploit the temperature-dependent dynamics of D(2)O confined in MCM-41. Samples with three pore sizes of 1.58, 2.03, and 2.34 nm and two D(2)O contents were investigated. The reorientation correlation times of confined D(2)O in variously sized pores exhibit different temperature dependencies. The results reveal that the D(2)O molecules at fast motion site remain mobile below approximately 225 K and a liquid-liquid phase transition occurs around this temperature for all samples studied. This temperature is thought to be unreachable for supercooled D(2)O. Particularly, in 20 wt % D(2)O loaded samples with pore diameters of 1.58 and 2.03 nm, the reorientational correlation times of D(2)O at fast motion site exhibit Arrhenius behavior between 225 and 290 K, while other samples show power law dependency. Thus, a liquid phase of the fragile type in bigger pores changes to the strong type in samples with smaller pores. 相似文献
990.
To deal with inhomogeneous diffusion coefficients of ions without altering the lattice spacing in the kinetic lattice grand canonical Monte Carlo (KLGCMC) simulation, an algorithm that incorporates diffusion coefficient variation into move probabilities is proposed and implemented into KLGCMC calculations. Using this algorithm, the KLGCMC simulation method is applied to the calculation of ion currents in a simple model ion channel system. Comparisons of ion currents and ion concentrations from these simulations with Poisson-Nernst-Planck (PNP) results show good agreement between the two methods for parameters where the latter method is expected to be accurate. 相似文献