Block copolymers of ethylene oxide and phenyl glycidyl ether: micellization, gelation, and drug solubilization

Three triblock copolymers of ethylene oxide and phenyl glycidyl ether, type E(m)G(n)E(m), where G = OCH2CH(CH2OC6H5) and E = OCH2CH2, were synthesized and characterized by gel-permeation chromatography, matrix-assisted laser desorption ionization time-of-flight mass spectrometry, and NMR spectroscopy. Their association properties in aqueous solution were investigated by surface tensiometry and light scattering, yielding values of the critical micelle concentration (cmc), the hydrodynamic radius, and the association number. Gel boundaries in concentrated micellar solution were investigated by tube inversion, and for one copolymer, the temperature and frequency dependence of the dynamic moduli served to confirm and extend the phase diagram and to highlight gel properties. Small-angle X-ray scattering was used to investigate gel structure. The overall aim of the work was to define a block copolymer micellar system with better solubilization capacity for poorly soluble aromatic drugs than had been achieved so far by use of block copoly(oxyalkylene)s. Judged by the solubilization of griseofulvin in aqueous solutions of the E(m)G(n)E(m) copolymers, this aim was achieved.     

Thermodynamics of micellization of tapered statistical copolymers of ethylene oxide and propylene oxide in water

Two tapered statistical copolymers were prepared by the oxyanionic polymerization of ethylene oxide and propylene oxide and characterized by gel permeation chromatography and 13C NMR spectroscopy. We denote the copolymers t-E/P38 and t-E/P30, where E = oxyethylene, OCH2CH2, and P = oxypropylene, OCH2CH(CH3), and the number denotes the mole percentage P. In each case the copolymer chain length was ca. 100 oxyalkylene units. The association of the copolymers to form micelles in aqueous solution was checked by dynamic light scattering. The critical micelle temperatures (cmt) of the copolymers at several concentrations were determined by static light scattering and dye solubilization, and values of the apparent standard enthalpy of micellization (DeltamicHapp0) were obtained. For both copolymers, a low value of DeltamicHapp0 was found when the copolymer concentration exceeded ca. 150 g dm(-3).     

Effect of copolymer architecture on the micellization and gelation of aqueous solutions of copolymers of ethylene oxide and styrene oxide

The micellar properties and solubilization capacity of poorly water soluble drugs of several micellar and gel solutions of diblock and triblock copolymers of styrene oxide/ethylene oxide have been measured and compared with block copolymers of butylene oxide/ethylene oxide, showing that the solubilization capacity of the styrene oxide block is approximately four times that of a butylenes oxide block for dilute solutions. To continue establishing the correlation between micellar characteristics and solubilization capacity, we have found it interesting to compare the micellar and gelation properties of the diblock and triblock copolymers PSO10PEO135 and PEO69PSO8PEO69 (subindexes are the number-average block lengths), with different architecture but similar average block lengths. Surface tension measurements allowed the determination of the critical micelle concentrations at several temperatures and, so, to calculate standard enthalpies of micellization. Static and dynamic light scattering data permitted us to determine micellar parameters and to obtain qualitatively the extent of hydration of the copolymer micelle. A tube inversion method was used to define the mobile-immobile (soft-hard gel) phase boundary. To refine the phase diagram and observe the existence of additional phases, rheological measurements were done. The results are in good agreement with previous values published for PSOnPEOm and PEOmPSOnPEOm copolymers.     

毛白杨环氧水解酶的异源表达及其在催化拆分手性环氧化物中的应用

对已公布的全基因组进行检索发现,杨树(Populus tomentosa)至少含有24个预测为可溶性环氧水解酶的基因.从中选取了7个可能的环氧水解酶基因进行克隆,通过扩增得到其中5个毛白杨(Populus tomentosa Carr)环氧水解酶基因.序列分析显示,它们与已克隆的巨大芽胞杆菌环氧水解酶的同源性仅为24%～26%.对该系列基因进行了在E.coli中的异源表达,并将得到的5个环氧水解酶(PTEH1～5)用于缩水甘油苯基醚和对硝基苯乙烯氧化物的酶促水解反应.结果发现,其中3个重组酶具有显著的环氧水解酶活性.进一步研究表明,PTEH1和PTEH2对于缩水甘油苯基醚显示了一定的反常规的(R)-选择性,而PTEH5则优先水解(S)-构型的缩水甘油苯基醚.因此,毛白杨中环氧水解酶表现出多样性.     

Facile allylic C-H bond activation on the bridging disulfide ligand in the Ru(III) dinuclear complex having a conjugated RuSSRu core

Treatment of [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)(mu-S(2))](CF(3)SO(3))(4) (1), which is prepared by the reaction of [[RuCl(P(OCH(3))(3))(2)](2)(mu-S(2))(mu-Cl)(2)] (2) with 4 equiv of AgCF(3)SO(3), with terminal alkenes such as 1-pentene, allyl ethyl ether, allyl phenyl ether, 1,4-hexadiene, and 3-methyl-1-butene, resulted in the formation of complexes carrying a C(3)S(2) five-membered ring, [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH(2)CH(2)CR(1)R(2)S]](CF(3)SO(3))(4) (3, R(1) = CH(2)CH(3), R(2) = H, 40%; 4, R(1) = OCH(2)CH(3), R(2) = H, 60%; 5, R(1) = OC(6)H(5), R(2) = H, 73%; 6, R(1) = CH=CHCH(3), R(2) = H, 48%; 7, R(1) = R(2) = CH(3), 40%). Reaction of 1 with methylenecycloalkanes was found to give several different types of products, depending on the ring size of the substrates. A trace of [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-SCH(CH(2)CH(2))CH(CH(3))S]](CF(3)SO(3))(4) (9) having a C(2)S(2) four-membered ring to bridge the two Ru atoms was obtained by the reaction of 1 with methylenecyclobutane, whereas the reaction with methylenecyclohexane gave [[Ru(P(OCH(3))(3))(2)(CH(3)CN)(3)](2)[mu-S(CH(2)(C=CHCH(2)CH(2)CH(2)CH(2))S)](CF(3)SO(3))(3) (10) in 69% yield via C-S bond formation and elimination of a proton. Throughout these reactions with alkenes giving a variety of products, the activation of the allylic C-H bond is always the essential and initial key step.     

Thermodynamic properties (enthalpy, bond energy, entropy, and heat capacity) and internal rotor potentials of vinyl alcohol, methyl vinyl ether, and their corresponding radicals

Vinyl alcohols (enols) have been discovered as important intermediates and products in the oxidation and combustion of hydrocarbons, while methyl vinyl ethers are also thought to occur as important combustion intermediates. Vinyl alcohol has been detected in interstellar media, while poly(vinyl alcohol) and poly(methyl vinyl ether) are common polymers. The thermochemical property data on these vinyl alcohols and methyl vinyl ethers is important for understanding their stability, reaction paths, and kinetics in atmospheric and thermal hydrocarbon-oxygen systems. Enthalpies , entropies , and heat capacities (C(p)()(T)) are determined for CH(2)=CHOH, C(*)H=CHOH, CH(2)=C(*)OH, CH(2)=CHOCH(3), C(*)H=CHOCH(3), CH(2)=C(*)OCH(3), and CH(2)=CHOC(*)H(2). Molecular structures, vibrational frequencies, , and C(p)(T) are calculated at the B3LYP/6-31G(d,p) density functional calculation level. Enthalpies are also determined using the composite CBS-Q, CBS-APNO, and G3 methods using isodesmic work reactions to minimize calculation errors. Potential barriers for internal rotors are calculated at the B3LYP/6-31G(d,p) level and used to determine the hindered internal rotational contributions to entropy and heat capacity. The recommended ideal gas phase values calculated in this study are the following (in kcal mol(-1)): -30.0, -28.9 (syn, anti) for CH(2)=CHOH; -25.6, -23.9 for CH(2)=CHOCH(3); 31.3, 33.5 for C(*)H=CHOH; 27.1 for anti-CH(2)=C(*)OH; 35.6, 39.3 for C(*)H=CHOCH(3); 33.5, 32.2 for CH(2)=C(*)OCH(3); 21.3, 22.0 for CH(2)=CHOC(*)H(2). Bond dissociation energies (BDEs) and group additivity contributions are also determined. The BDEs reveal that the O-H, O-CH(3), C-OH, and C-OCH(3) bonds in vinyl alcohol and methyl vinyl ether are similar in energy to those in the aromatic molecules phenol and methyl phenyl ether, being on average around 3 kcal mol(-1) weaker in the vinyl systems. The keto-enol tautomerization enthalpy for the interconversion of vinyl alcohol to acetaldehyde is determined to be -9.7 kcal mol(-1), while the activation energy for this reaction is calculated as 55.9 kcal mol(-1); this is the simplest keto-enol tautomerization and is thought to be important in the reactions of vinyl alcohol. Formation of the formyl methyl radical (vinoxy radical/vinyloxy radical) from both vinyl alcohol and methyl vinyl ether is also shown to be important, and its reactions are discussed briefly.     

Preparation and solution behavior of a thermoresponsive diblock copolymer of poly(ethyl glycidyl ether) and poly(ethylene oxide)

A thermoresponsive diblock copolymer, poly(ethyl glycidyl ether)-block-poly(ethylene oxide) (PEGE-b-PEO), is synthesized by successive anionic ring-opening polymerization of ethyl glycidyl ether and ethylene oxide using 2-phenoxyethanol as a starting material, and its solution behavior is elucidated in water. In a dilute 1 wt % solution, the temperature-dependent alteration in the polymer hydrodynamic radius (RH) is measured in the temperature range between 5 and 45 degrees C by pulse-gradient spin-echo NMR and dynamic light scattering. The RH value increased with temperature in two steps, where the first step at 15 degrees C corresponds to the core-shell micelle formation and the second step at 40 degrees C corresponds to the aggregation of the core-shell micelles. The formation of the core-shell micelles is supported by the solubilization of a dye (1,6-diphenyl-1,3,5-hexatriene) in the hydrophobic core, which is recognized for a copolymer solution in the temperature range between 20 and 40 degrees C. In this temperature range, the core-shell micelles and the unimers coexist and the fraction of the former gradually increases with increasing temperature, suggesting equilibrium between the micelles and the unimers. In the concentrated regime (40 wt % solution), the solution forms a gel and the small-angle X-ray scattering measurements reveal the successive formation of hexagonal and lamellar liquid crystal phases with increasing temperature.     

取代苯醌在乙腈中的电化学和光谱电化学研究

研究了含有甲基、甲氧基、氟或氯等不同取代基的对苯醌衍生物在乙腈中的电化学和紫外-可见光谱电化学性质,并探讨了取代基对化合物电化学性质的影响.结果表明,每个化合物均可以发生两步可逆的单电子还原反应,分子中的供电子基能使还原反应电位发生负移,而吸电子基则可使电位发生正移.还原电位的变化值(ΔE)与取代基哈密特常数(∑σ)之间呈线性关系,其方程为:ΔE1=0.386 9∑σ-0.073 5(V),R2=0.996,ΔE2=0.280 3∑σ-0.114 5(V),R2=0.981.在控制电位还原时化合物的紫外可见光谱具有明显的变化,表明两步还原反应的产物分别为阴离子自由基(R)nQ.-和负二价阴离子(R)nQ2-(R=—CH3,—OCH3,—Cl,—F;n=0～4).     

开链冠醚类似物的合成与研究I

Antipyrine derivatives I (Z = O, S; Z1 = CH2, CH2OCH2; n = 0, 1, 2, 3) were prepared as open-chain crown ether analogs. Thus, refluxing diethylene glycol ditosylate with 4-hydroxyantipyrine and K2CO3 in acetone for 15 h gave I (Z = O, Z1 = CH2OCH2). The activities of I as phase-transfer catalyst for iodination of 1-bromoctane with NaI, or KI were reported.     

Analysis of the intermolecular interactions between CH3OCH3, CF3OCH3, CF3OCF3, and CH2F2, CHF3

The intermolecular interaction energy curves of CH(3)OCH(3)-CH(2)F(2), CF(3)OCH(3)-CH(2)F(2), CF(3)OCF(3)-CH(2)F(2), CH(3)OCH(3)-CHF(3), CF(3)OCH(3)-CHF(3), and CF(3)OCF(3)-CHF(3) complexes were calculated by the MP2 level ab initio molecular orbital method using the 6-311G** basis set augmented with diffuse polarization functions. We investigate the fluorine substitution effects of both methane and dimethyl ether on intermolecular interactions. In addition, orientation dependence of intermolecular interaction energies is also studied with utilizing eight types of orientations. Our analyses demonstrate that partial fluorinations of methane make electrostatic interaction dominant, and consequently enhance attractive interaction at several specific orientations. On the contrary, fluorine substitutions of dimethyl ether substantially decrease the electrostatic interaction between ether and CH(2)F(2) or CHF(3); thus, there is no such characteristic interaction between the C-H of fluorinated methane and ether oxygen of CF(3)OCF(3) as conventional hydrogen bonding, due to reduced polarity of fluorinated ether. The combination of different pairs of the electrostatic interaction is therefore responsible for the intermolecular interaction differences among the complexes investigated herein and also their orientations.     

Synthesis,micellization and gelation of temperature‐responsive star‐shaped block copolymers

A series of amphiphilic temperature‐responsive star‐shaped poly(D,L‐lactic‐co‐glycolic acid)‐b‐methoxy poly(ethylene glycol) (PLGA‐mPEG) block copolymers with different arm numbers were synthesized via the arm‐first method. Gel permeation chromatography data confirmed that star‐shaped PLGA‐mPEG copolymers had narrow polydispersity index, indicating the successful formation of star‐shaped block copolymers. Indirectly, the ¹H NMR spectra in two kinds of solvents and dye solubilization method had confirmed the formation of core‐shell micelles. Further, core‐shell micelles with sizes of about 30–50 nm were directly observed by transmission electron microscopy. Subsequently, the micellar sizes and distributions as a function of concentrations and temperature were measured. At various copolymer concentrations, individual micelles with size of 20–40 nm and grouped micelles with size of 600–700 nm were found. Micellar mechanism of star‐shaped block copolymers in aqueous solution was simultaneously discussed. In addition, sol–gel transition of star‐shaped block copolymers in water was also investigated via the inverting test method. The critical gel temperature (CGT) and critical gel concentration (CGC) values of two‐arm, three‐arm and four‐arm copolymer solutions were markedly higher than ones of one‐arm copolymer. Moreover, the same CGC values of copolymer solution with different molecular weight and the same arm composition were ~15 wt %, and CGT values increased from ~38 to ~47°C with increasing arm numbers. Finally, the temperature‐dependent micellar packing gelation mechanism of star‐shaped block copolymer was schematically illustrated. Copyright © 2013 John Wiley & Sons, Ltd.     

Aggregation and thermoresponsive properties of new star block copolymers with a cholic acid core

Poly(allyl glycidyl ether) (PAGE) and poly(ethylene glycol) (PEG) blocks were sequentially grown via anionic polymerization to form four block copolymer arms on a cholic acid (CA) core, yielding star block copolymers (CA(AGE(8)-b-EG(n))(4)) with low polydispersities (ca. 1.05). The introduction of PAGE segments into CA(PEG)(4) significantly reduced their crystallinity. The polymers can aggregate in water at room temperature above their critical aggregation concentration. The copolymers are thermoresponsive; their behavior in aqueous solutions was studied by the use of UV-visible spectroscopy, dynamic light scattering, and transmission electron microscopy. Their cloud points vary from 13 to 55 °C with increasing length of the PEG segments. Double thermoresponsive behavior was observed with short PEG segments because of a two-step transition process: small micelles are formed upon heating and then further aggregate into micellar clusters through the association of PEG chains.     

五羰基锰烷基化合物的合成及光化学反应研究

用五羰基锰钾盐和相应的卤代物在乙醚中的金属化反应合成了五羰基锰烷基合物 (CO)5MnR（R = CH3,p-CH2C6H4CH3, p-CH2C6H4OCH3 ）,产率达到72-93％,将这些化合物与1-2当量(CH3)2(C6H5)SiH和(CH3)(C6H5)2SiH的C6D6溶液在5℃光解,分别得到五羰基锰硅烷基化合物(CO)5MnSi(C6H5)(CH3)2和(CO)5MnSi(C6H5)2(CH3)（产率达到70-88％）。在光化学反应中,还观察到相应甲烷,对二甲苯,和对甲基苯甲醚的定量生成,以及少量的Mn2(CO)10（<2％-4％）,(CO)4MnH(SiR3)2（<9%）副产物。     

乙二醇甲醚中电解锡电解液直接水解制备纳米SnO2

采用锡金属为阳极，在无隔膜电解槽中，电化学溶解锡于乙二醇甲醚中制备得到纳米SnO2前驱体Sn(OCH2CH2OCH3)4，将电解液直接水解经溶胶-凝胶法制备纳米SnO2，前驱体通过拉曼和红外光谱进行表征.纳米SnO2采用X射线粉末衍射(XRD)和透射电子显微镜(TEM)进行表征.实验表明,电解合成的Sn(OCH2CH2OCH3)4能够溶解于乙醇中, 适宜作为溶胶-凝胶(sol-gel)法制备纳米SnO2的原料，制得的纳米SnO2经600 ℃煅烧后呈球形单分散结构，晶型为四方锡石型, 比表面为62.58 m2·g－1，平均粒径在(10.0±0.4) nm左右.产率为89.3％，电流效率为86.9％.