Ion channel behavior of amphotericin B in sterol-free and cholesterol- or ergosterol-containing supported phosphatidylcholine bilayer model membranes investigated by electrochemistry and spectroscopy

Amphotericin B (AmB) is a popular drug frequently applied in the treatment of systemic fungal infections. In the presence of ruthenium (II) as the maker ion, the behavior of AmB to form ion channels in sterol-free and cholesterol- or ergosterol-containing supported phosphatidylcholine bilayer model membranes were studied by cyclic votammetry, AC impedance spectroscopy, and UV/visible absorbance spectroscopy. Different concentrations of AmB ranging from a molecularly dispersed to a highly aggregated state of the drug were investigated. In a fixed cholesterol or ergosterol content (5 mol %) in glassy carbon electrode-supported model membranes, our results showed that no matter what form of AmB, monomeric or aggregated, AmB could form ion channels in supported ergosterol-containing phosphatidylcholine bilayer model membranes. However, AmB could not form ion channels in its monomeric form in sterol-free and cholesterol-containing supported model membranes. On the one hand, when AmB is present as an aggregated state, it can form ion channels in cholesterol-containing supported model membranes; on the other hand, only when AmB is present as a relatively highly aggregated state can it form ion channels in sterol-free supported phosphatidylcholine bilayer model membranes. The results showed that the state of AmB played an important role in forming ion channels in sterol-free and cholesterol-containing supported phosphatidylcholine bilayer model membranes.

Preparation and characterization of PSt-b-PHEMA metal hybrids

The block copolymer polystyrene-b-poly[2-(trimethylsilyloxy)ethylene methacrylate] (PSt-b-PTMSEMA) was synthesized using atom-transfer radical polymerization (ATRP). The hydrolysis of PSt-b-PTMSEMA led to the formation of an amphiphilic block copolymer, polystyrene-b-poly(2-hydroxylethyl methacrylate) (PSt-b-PHEMA), which was characterized by GPC and H-1-NMR. TEM showed that the PSt-b-PHEMA formed a micelle, which is PSt as the core and PHEMA as the shell. Under appropriate conditions, the nickel or cobalt ion cause chemical reactions in these micelles and could be reduced easily. ESCA analysis showed that before reduction the metal existed as a hydroxide; after reduction, the metal existed as an oxide, and the metal content of these materials on the surface is more than that on the surface of the copolymer metal ion. XRD analysis showed that the metal existed as a hydroxide before reduction and existed as a metal after reduction.

Observation of inverted phases in poly(styrene-b-butadiene-b-styrene) triblock copolymer by solvent-induced order-disorder phase transition

We report observation of inverted phases consisting of spheres and/or cylinders of the majority fraction block in a poly(styrene-b-butadiene-b-styrene) (SBS) triblock copolymer by solvent-induced order-disorder phase transition (ODT). The SBS sample has a molecular weight of 140K Da and a polystyrene (PS) weight fraction of 30%. Tapping mode atomic force microscopy (AFM) and transmission electron microscopy (TEM) were utilized to study the copolymer microstructure of a set of solution-cast SBS films dried with different solvent evaporation rates, R. The control with different R leads to kinetic frozen-in of microstructures corresponding to a different combination parameter chi (eff)Z of the drying films (where chi (eff) is the effective interaction parameter of the polymer solution in the cast film and Z the number of "blobs" of size equal to the correlation length one block copolymer chain contains), for which faster evaporation rates result in microstructures of smaller chi (eff)Z. As R was decreased from rapid evaporations (similar to0.1 mL/h), the microstructure evolved from a totally disordered one sequentially to inverted phases consisting of spheres and then cylinders of polybutadiene (PB) in a PS matrix and finally reached the equilibrium phase, namely cylinders of PS in a PB matrix. We interpret the formation of inverted phases as due to the increased relative importance of entropy as chi (eff)Z is decreased, which may dominate the energy penalty for having a bigger interfacial area between the immiscible blocks in the inverted phases.

VUV excitation properties of LnAl(3)B(4)O(12): Re (Ln = Y, Gd; Re=Eu, Tb)

Vacuum ultraviolet excitation spectra of LnAl(3)B(4)O(12):Re (Ln = Y, Gd; Re = Eu, To), along with X-ray photoelectron spectra, were measured. The spectra are tentatively interpreted in terms of the optical properties of the rare earth ions and the band structure. It was found that there is an energy transfer from the hosts to the rare earth ions. It was also found that the top of the valence band in the Gd compound is mainly formed by the 2p levels of O2- and the 4f levels of Gd3+, and in the Y compound mainly by the 2p levels of O2-. (C) 2000 Elsevier Science Ltd. All rights reserved.

一些含半夹心结构ⅥB族金属的1,1’-二硫(硒)二茂铁化合物的合成

CpCr(NO)(CO)_2与Fe(C_5H_4S)_2S反应,形成氧化-还原产物CpCr(NO)(SC_5H_4)_2Fe(1)。双杂核二茂铁化合物CpM(NO)(EC_5H_4)_2Fe[M=Mo,E=S(2a),Se(2b);M=W,E=S(4a),Se(4b)]、CpMo(NO)(SC_5H_4)_2Fe(3)、Cp_2Mo(SeC_5H_4)_2Fe(6)和Cp_2W(SC_5H_4)_2Fe(7)可通过Fe(C_5H_4ELi)_2·2THF(E=S,Se)与CpM(NO)I_2(M=Mo,W)、[CpMo(NO)I_2]_2或Cp_2MCl_2(M=Mo,W)反应制得。三核杂原子二茂铁化合物[CpCr(NO)_2]_2(EC_5H_4)_2Fe[E=S(8a),Se(8b)],由Fe(C_5H_4ELi)_2·2THF(E=S,Se)与二倍摩尔量的CpCr(NO)_2I反应制备。通过AgBF_4氧化2a得到二茂铁离子型化合物[CpMo(NO)(SC_5H_4)_2Fe]~+BF_4~-(5)。采用元素分析、红外光谱、~1H和~(13)C NMR谱以及EI-MS表征了所合成的新型化合物。

ABF_3:Eu,Gd(A:K,Li;B:Ba,Mg)中Gd~(3+)→Eu~(2+)的能量传递

通过高温固相反应法,在高纯N_2气氛中合成了BaLiF_3,KMgF_3中单掺和双掺Eu,Gd的ABF_3型复合氟化物。研究了各类掺杂体系的光谱特性,观察到了Gd~(3+)→Eu~(2+)的能量传递,分析了能量传递过程,探讨了能量传递机理,并讨论了Gd~(3+)和Eu~(2+)的取代格位。

Circular dichroism spectro electrochemical and voltammetric studies of vitamin B-2

Electroreduction of vitamin B-2 (VB2) was studied by in situ circular dichroism (CD) spectroelectrochemistry (SEC) with a long optical path length thin layer cell (LOPLTLC). The results showed that the electroreduction of VB2 in phosphate buffer solution (PBS) (PH 6.8) was a two-electron electrochemical process with weak adsorption of the reactant at the glassy carbon (GC) electrode surface. The CD spectra change of VB2 in the reduction process was explained with the theory of electronic states. We also treated the CD spectra with a singular value decomposition least square (SVDLS) method, and have found not only the number of components and their spectra, but also the fraction distribution of each component in the electroreduction process of VB2.

Controlled synthesis of L-lactide-b-epsilon-caprolactone block copolymers using a rare earth complex as catalyst

Well-defined block copolymers of L-lactide-b-epsilon-caprolactone were synthesized by sequential polymerization using a rare earth complex, Y(CF3COO)(3)/Al(iso-Bu)(3), as catalyst system. The compositions of the block copolymers could be adjusted by manipulating the feeding ratio of comonomers. The characterizations by GPC, H-1 NMR, C-13 NMR, and DSC displayed that the block copolymer, poly(epsilon-caprolactone-b-L-lactide) [P(CL-b-LLA)], had a narrow molecular weight distribution and well-controlled sequences without random placement.

Mechanism-transformation synthesis and characterization of poly(styrene-b-2-ethyl-2-oxazoline) diblock copolymer

By mechanism-transformation (anionic --> cationic) poly(styrene-6-2-ethyl-2-oxazoline) diblock copolymer, PS-b-PEOx, was synthesized in two steps. The first step is the polymerization of styrene block capped with ethylene oxide and its tosylation; the second step is the cationic ring-opening polymerization of 2-ethyl-2-oxazoline. The products were thoroughly characterized by various methods, such as H-1-NMR, IR, DMA, TEM and SAXS. The results show that the copolymer obtained possesses high molecular weight and narrow molecular weight distribution.