Self-assembly and emulsification of poly{[styrene-alt-maleic acid]-co-[styrene-alt-(N-3,4-dihydroxyphenylethyl-maleamic acid)]}

Self-assembled polymeric micelles can be used as efficient particulate emulsifiers. To explore the relationship between the structure and the oil-water interfacial behavior of the micelle emulsifiers, a new type of amphiphilic random copolymer, poly{(styrene-alt-maleic acid)-co-[styrene-alt-(N-3,4-dihydroxyphenylethyl-maleamic acid)]} (SMA-Dopa), was synthesized, self-assembled into micelles, and used as emulsifiers. SMA-Dopa was synthesized via an aminolysis reaction between dopamine and commercial alternating copolymer poly(styrene-alt-maleic anhydride) (SMA). Dopamine moiety facilitated the self-assembly of the SMA-Dopa in selective-solvent into stable micelles, and increased the adsorption of the SMA-Dopa at the oil-water interface. Additionally, the structural transition of the self-assembled SMA-Dopa52 micelles in response to pH and salinity changes were confirmed by means of TEM, AFM, DLS, aqueous electrophoresis techniques, potentiometric titration, and pyrene fluorescence probe methods. Micelles shrunk with increasing salinity, and flocculation of the shrunken primary micelles occurred at salt concentration exceeding 0.1 M. The micelles swelled with increasing pH, and the disassociation of the SMA-Dopa52 micelles occurred at pH above approximately 6.5. The structure of the micelles plays a crucial role in the oil-water interfacial performance. Micelles with various structures were used as emulsifiers to adsorb at the styrene-water and toluene-water interfaces. The emulsifying characteristics demonstrated that self-assembled SMA-Dopa52 micelles with moderately swollen structure (at 2 < pH < 6) combine the advantages of the solid particulate emulsifiers and polymeric surfactants, possessing excellent emulsifying efficiency and good emulsion stability. Moreover, the emulsifying performance of the SMA-Dopa52 micelles could be enhanced by the addition of salt.     

Observation of photocatalytic dissociation of water on terminal Ti sites of TiO2(110)-1 × 1 surface

The water splitting reaction based on the promising TiO(2) photocatalyst is one of the fundamental processes that bears significant implication in hydrogen energy technology and has been extensively studied. However, a long-standing puzzling question in understanding the reaction sequence of the water splitting is whether the initial reaction step is a photocatalytic process and how it happens. Here, using the low temperature scanning tunneling microscopy (STM) performed at 80 K, we observed the dissociation of individually adsorbed water molecules at the 5-fold coordinated Ti (Ti(5c)) sites of the reduced TiO(2) (110)-1 × 1 surface under the irradiation of UV lights with the wavelength shorter than 400 nm, or to say its energy larger than the band gap of 3.1 eV for the rutile TiO(2). This finding thus clearly suggests the involvement of a photocatalytic dissociation process that produces two kinds of hydroxyl species. One is always present at the adjacent bridging oxygen sites, that is, OH(br), and the other either occurs as OH(t) at Ti(5c) sites away from the original ones or even desorbs from the surface. In comparison, the tip-induced dissociation of the water can only produce OH(t) or oxygen adatoms exactly at the original Ti(5c) sites, without the trace of OH(br). Such a difference clearly indicates that the photocatalytic dissociation of the water undergoes a process that differs significantly from the attachment of electrons injected by the tip. Our results imply that the initial step of the water dissociation under the UV light irradiation may not be reduced by the electrons, but most likely oxidized by the holes generated by the photons.     

Relation between the permeability and the degree of coil overlap of polymer in the bulk state

Based on the expression of the index of coil interpenetration (i.e.,the degree of coil overlap,ξ_b) of amorphous polymers in the bulk state proposed by Qian,theξ_b was rewritten asξ_b=ρ_b[η]_θ/1.66 via Flory's intrinsic viscosity equation at them conditions.Theξ_b ofpoly (vinyl chloride) (PVC) dense membranes with different molecular weights and cellulose diacetate (CA) dense membranes prepared using different solvents were determined.The permeability,permeation coefficient (P) of nitrogen and permeation flux (J) of liquid through both membranes,respectively,was measured.P and J decreased exponentially with increasingξ_b for PVC and CA membranes were revealed.     

2-（2＇-羟基-3’-甲氧基苯基）-5，6-二硝基苯并咪唑的阴离子识别

设计并合成了2-（2’-羟基-3’-甲氧基苯基）-5，6-二硝基苯并咪唑化合物（1），通过X射线单晶衍射研究了该化合物的固态结构．利用紫外-可见光谱技术研究了其对阴离子的识别，发现化合物1能够在DMSO中对AcO^-，H2PO4^-，OH^-的3种离子进行有效识别，同时溶液由原来的黄色变成红色，实现裸眼检测．     

β-环糊精与水杨酸包合物的合成与结构

合成了β-环糊精与水杨酸的包合物b-cyclodextrin-salicylic acid (β-CD-sal) [(C₄₂H₇₀O₃₅)₂•(C₇H₆O₃)₂•(H₂O)₂₄], 用X射线单晶衍射、元素分析和核磁共振对其分子结构进行了表征. X射线单晶衍射结果表明: 包合物的晶体属于单斜晶系, 空间群为C₂, a＝1.9269(5) nm, b＝2.4395(7) nm, c＝1.6095(4) nm, β＝107.816(5)°, V＝7.203(3) nm³, Z＝4, D_c＝1.373 g•cm^－3, F(000)＝3176, R[I＞2σ(I)]＝0.0971. 在形成的2∶2包合物中, β-环糊精通过羟基间的氢键形成头对头的二聚体, 两个水杨酸分子以不同的形式与环糊精形成包合物, 其中一个水杨酸分子寄居于环糊精的空腔中, 而另一个水杨酸则位于由两个环糊精形成二聚体的空隙中.     

纳米铜薄膜氧化反应动力学规律研究

研究了140 ℃下纳米尺度Cu薄膜的氧化行为. 采用真空蒸发法以不同沉积速率制备一系列Cu薄膜, 利用原子力显微镜(AFM)观察其微观形貌, 选取形貌良好的Cu薄膜样品. 采用方块电阻和透射光谱两种方法为表征手段, 测量16～22 nm范围内不同厚度Cu薄膜在140 ℃下完全氧化所需要的时间, 得到了Cu薄膜氧化反应的动力学曲线, 并利用X射线衍射(XRD)分析了氧化产物的晶相结构和成分. 结果表明, 纳米尺度下Cu薄膜在140 ℃下氧化反应的动力学表征结果满足特殊的反对数生长规律, 反应产物为Cu₂O.     

Efficient dehalogenation of polyhalomethanes and production of strong acids in aqueous environments: water-catalyzed O--H-insertion and HI-elimination reactions of isodiiodomethane (CH2I-I) with water

A combined experimental and theoretical study of the ultraviolet photolysis of CH2I2 in water is reported. Ultraviolet photolysis of low concentrations of CH2I2 in water was experimentally observed to lead to almost complete conversion into CH2(OH)2 and 2HI products. Picosecond time-resolved resonance Raman spectroscopy experiments in mixed water/acetonitrile solvents (25%-75% water) showed that appreciable amounts of isodiiodomethane (CH2I-I) were formed within several picoseconds and the decay of the CH2I-I species became substantially shorter with increasing water concentration, suggesting that CH2I-I may be reacting with water. Ab initio calculations demonstrate the CH2I-I species is able to react readily with water via a water-catalyzed O--H-insertion and HI-elimination reaction followed by its CH2I(OH) product undergoing a further water-catalyzed HI-elimination reaction to make a H2C=O product. These HI-elimination reactions produce the two HI leaving groups observed experimentally and the H2C=O product further reacts with water to produce the other final CH2(OH)2 product observed in the photochemistry experiments. These results suggest that CH2I-I is the species that reacts with water to produce the CH2(OH)2 and 2HI products seen in the photochemistry experiments. The present study demonstrates that ultraviolet photolysis of CH2I2 at low concentration leads to efficient dehalogenation and release of multiple strong acid (HI) leaving groups. Some possible ramifications for the decomposition of polyhalomethanes and halomethanols in aqueous environments as well as the photochemistry of polyhalomethanes in the natural environment are briefly discussed.     

Simultaneous determination of ropivacaine and antipyrine by high performance liquid chromatography and its application to the in vitro transplacental study

A simple and reliable RP-HPLC method has been developed for the simultaneous determination of ropivacaine and antipyrine in perfusate samples. Samples were analyzed on an ODS column with UV detection at 210 nm after liquid-liquid extraction. The mobile phase consisted of potassium dihydrogenphosphate (25 mM, adjusted to pH 5.0 with phosphoric acid)-acetonitrile (79:21, v/v). The method has been validated to be precise, accurate and linear. It has been applied to the investigation of placental transfer of ropivacaine via a dually perfused cotyledon model of human placenta in vitro.     

Solution redox chemistry of carbon nanotubes

UV/vis/NIR absorbance spectra were used to monitor electron transfer between small-molecule redox reagents and carbon nanotubes (CNTs). The oxidation of (6, 5)-enriched nanotubes in water with K(2)Ir(Cl)(6) reveals a valence electron density of 0.2-0.4 e(-)/100 carbon atoms and a reduction potential of approximately 800 mV versus NHE. The reduction potential of CNTs is found to increase with increasing band gap and to decrease with the introduction of an anionic dispersant. In light of this newly revealed redox chemistry of CNTs, we propose that the previously observed bleaching of the CNT absorbance spectrum at low pH is most likely a consequence of the oxidation of the nanotubes by oxygen. These results demonstrate facile oxidation and reduction of CNTs, provide a way to quantify the population of valence electrons, and point to possible applications of CNT in the catalysis of redox reactions.     

Synthesis and structures of beta-diketiminatotin(II) halides, an amide and of Sn(=E)[{N(R)C(Ph)}2CH](NR2) (E = S or Se, R = SiMe3)

Treatment of [Li(L1)]2 (1) or K(L2) (2) with SnX2 in Et2O yielded the heteroleptic beta-diketiminatotin(II) halides Sn(L1)Cl (3a), Sn(L1)Br (3b) or Sn(L2)Cl (4), even when an excess of the alkali metal beta-diketiminate was used [L1={N(R)C(Ph)}2CH, L2={N(R)C(Ph)CHC(But)N(R)}, R = SiMe3]. From and half an equivalent each of SnCl2.2H2O and SnCl2, or one equivalent of SnCl2.2H2O, the product was Sn(L3)Cl (5) or Sn(L4)Cl (6), in which one or both of the N-R bonds of L1 had been hydrolytically cleaved; the compound Sn(L5)Cl (7) was similarly obtained from and an equivalent portion of SnCl2.2H2O [L3={N(R)C(Ph)CHC(But)N(H)}, L4={N(H)C(Ph)CHC(But)N(H)} and L5={N(H)C(Ph)}2CH]. The halide exchange between 3a and 3b, studied by two-dimensional (119)Sn{1H}-NMR spectroscopy, is attributed to implicate a (mu-Cl)(mu-Br)-dimeric intermediate or transition state. The 13C{1H}-NMR spectra of or showed two distinct resonances for each group, which coalesced on heating, corresponding to DeltaG(338 K)= 69.4 (3a) or 72.8 (3b) kJ mol(-1). The chloride ligand of was readily displaced by treatment with NaNR2, CF3SO3H or CH2(COPh)2, yielding Sn(L1)X [X = NR2 (8), O3SCF3 (9) or {OC(Ph)}2CH (10)]. Oxidative addition of sulfur or selenium to gave the tin(IV) terminal chalcogenides Sn(E)(L1)(NR2)[E = S (11) or Se (12)]. The X-ray structures of the cocrystal of 3a/3b and of the crystalline compounds 5, 6, 8, 11 and are presented, as well as multinuclear NMR spectra of each of the new compounds.