H型(PS)2PEG(PS)2嵌段共聚物在旋涂过程中的结晶行为

采用原子力显微镜和X射线衍射等手段研究了H型(PS)₂PEG(PS)2嵌段共聚物在不同溶剂和不同浓度的溶液中旋涂所得薄膜的形貌, 并与聚乙二醇(PEG)均聚物进行了比较. 虽然(PS)₂PEG(PS)₂中PS的链长很短, 但对形貌有很大影响, PS链段的存在改变了聚合物在基底上的稳定性, 使用四氢呋喃为溶剂, 当溶液浓度较小时, 在旋涂过程中发生去润湿, 然后再发生结晶, 膜厚较大时去润湿被抑止, 所得形貌与PEG均聚物类似. 以甲苯为溶剂时, 由于PEG和PS与溶剂的相互作用不同, 共聚物在溶液中形成胶束, 从而改变了聚合物的结晶形貌.     

Zur Bestimmung von Pipecolins?ure (PS) in biologischem Material

Ohne Zusammenfassung     

Die quantitative Mikrobestimmung von Phenylbrenztraubens?ure (PS) im Harn

Ohne Zusammenfassung     

高浓度LaCl3抑制黄瓜(Cucumis sativus Linn)光系统Ⅱ(PS Ⅱ)活性

研究了高浓度LaCl3对黄瓜（Cucumis sativus Linn）光系统Ⅱ（PSⅡ）光诱导荧光动力学参数、低温荧光光谱和放氧活性的影响。结果表明，随着黄瓜体内LaCl3浓度的升高、其荧光量子产率、PSⅡ最大光化学效率、放氧活性和电子传递速率都明显降低。低温荧光分析表明，低浓度LaCl3引起激发能更多的分配给PSⅡ。高浓度LaCl3对黄瓜幼茁的抑制作用表现在对类囊体膜结构的破坏。进而导致PSⅡ光合活性下降，并最终抑制黄瓜生长。     

光系统Ⅱ(PSⅡ)抑制剂的比较分子场研究

以光系统Ⅱ抑制剂DISCO(DIStanceCOmparisons)模型的活性构象分子作为模板,利用比较分子场分析方法对三类结构不同的化合物进行了三维构效关系的研究。研究结果有助于对DISCO重叠模型的评估的新型PSⅡ抑制剂的设计与合成。     

STUDY ON THE POLING PROPERTIES OF NONLINEAR OPTICAL ACTIVE DERIVATIVE OF POLY (p-HYDROXYSTYRENE):(PS)O-DCV

In this paper, the poling properties of (PS)O-DCV, a derivative of poly (p-hydroxystyrene ), was reported. The investigations showed that the thermochromism correction, which was neglected in the literatures, should be considered in the measurements of order parameter of poled films with electrochromism technique Here, another linear optical method, IR and polarized IR spectra for characterizing of poled films was suggested first time. The bulk second nonlinear optical coefficient d_(33) of poled films could be estimated by measured order parameter semi-qualitatively.     

T(4-Mop)PS4卟啉与牛血清蛋白相互作用的研究

以四-(4-甲氧基-3-磺酸基苯)卟啉(T(4-Mop)PS4)为探针,通过T(4-Mop)PS4与牛血清白蛋白(BSA)的相互作用,建立了测定BSA的电化学分析方法。T(4-Mop)PS4的峰电流变化(ΔIp)与BSA在2.0×10-6～1.0×10-5mol.L-1范围内呈良好的线性关系,检出限为1.2×10-6mol.L-1;对5.0×10-6mol.L-1BSA平行测定8次,其相对标准偏差为2.0%,回收率为95%～104%。组氨酸、缬氨酸、苯丙氨酸、丝氨酸、异白氨酸、谷氨酰胺、苏氨酸等氨基酸对BSA的测定不产生干扰。采用紫外可见光度法、荧光光谱法和线性扫描伏安法(LSV)研究了T(4-Mop)PS4与BSA之间的相互作用,并测定了二者相互作用的结合常数和结合比。研究表明,T(4-Mop)PS4与BSA之间主要以疏水作用力结合,形成了1∶1的稳定复合物。     

Synthesis and Self-Assembly Behaviors of Four-Arm Star Block Copolymers Poly(ϵ-caprolactone)-b-poly(2- (diethylamino) ethyl methacrylate)) in Aqueous Solution

Four-arm star block polymers consisting of hydrophobic poly(?-caprolactone) (PCL) block and hydrophilic poly(2-(diethylamino) ethyl methacrylate)) (PDEAEMA) block were successfully synthesized by ring opening polymerization (ROP) and atom transfer radical polymerization (ATRP). Chain lengths of PDEAEMA segments were varied to obtain a series of star copolymers with different hydrophilic/hydrophobic ratio, which were desired for self-assembly study. Dynamic light scattering (DLS) and transmission electron microscopic (TEM) were used to study their self-assembly behavior. In the PBS solution with different pH value, the star polymers formed micelles or nanoparticles. Furthermore, the morphologies of the micelles were also pH-dependent. Critical micelle concentrations of star copolymers changed from 5.0 to 17.5 mg/L with the increase of hydrophilic block length or the pH decrease. Moreover, a steady increase was found on the micelles diameters when the pH decreased from 7.0 to 3.0. The low CMC value and slight changes on micelle diameter indicated that the micelle remained stable under the changing external stimulus.     

The Synthesis of Star Style Metaloporphyrin

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Multiarm Star Poly(ε-caprolactone) with Hyperbranched Polyamidoamine as Core Capable of Selective Accommodating Cationic or Anionic Guests

Hyperbranched polyamidoamines(HPAs) were directly employed as macroinitiators to initiate the Sn(Oct)2 catalyzed ring-opening polymerization of ε-caprolactone(CL), resulting in multiarm star copolymers with poly(ε-caprolactone)(PCL) as shells and HPA as core(HPA-b-PCL). From 1H-NMR characterization it was deduced that both the primary amines and the secondary amide groups of HPAs could initiate the CL polymerization, and the initiation efficiency increased when more CL monomers were fed. The average arm-numbers of the obtained stars were in the range of 115-353. Differential scanning calorimetry measurements demonstrated that the melting and crystallization temperatures, fusion and crystallization enthalpy and the degree of crystallinity of the star polymers increased as the PCL arm length increased. HPAb-PCL stars could be used as nanocarriers to efficiently accommodate anionic dyes at acidic condition, while load cationic dyes at basic condition. Compared with the dye-loading behavior of multiarm star PCL with the neutral hyperbranched polyglycerol as core, it was deduced that HPA-b-PCL nanocarriers accommodated anionic dyes using the HPA core, while loaded cationic dyes using both the HPA core and the PCL shell. Dynamic light scattering analyses also supported such deduction. Furthermore, HPA-b-PCL nanocarriers could selectively load the anionic Eosin Y or the cationic methylene blue from their mixture at p H = 6 or 9, respectively, realizing their separation.     

The synthesis of the [Fe(Phen)3](iso-Bu2PS2)2 Complex. The crystal structures of [Fe(Phen)3](iso-Bu2PS2)2 · 5H2O and disulfan {iso-Bu2P(S)S}2

The complex [Fe(Phen)₃][iso-Bu₂PS₂)₂ (I) was synthesized and the single crystals of [Fe(Phen)₃](iso-Bu₂PS₂)₂ · 5H₂O (II) were grown. The disulfan {iso-Bu₂P(S)S}₂ (III) was isolated. Compound II consists of the complex cations [Fe(Phen)₃]²⁺, the outer-sphere anions iso-Bu₂PS ₂ ^? , and the molecules of water of crystallization. The coordination polyhedron of the Fe atom is a distorted N₆ octahedron. Complex I is diamagnetic, and thus, the full spin of the Fe²⁺ ion S = 0. The structure of III is built of the molecules containing the S-S bridge 2.061(1) Å in length.     

Synthesis and Characterization of Four-Arm Star Poly(ϵ-caprolactone)-Block-Poly(cyclic-carbonate methacrylate) Copolymers by Combining Ring-Opening Polymerization With Atom Transfer Radical Polymerization

Well-defined four-arm star poly(?-caprolactone)-block-poly(cyclic carbonate methacrylate) (PCL-b-PCCMA) copolymers were synthesized by combining ring-opening polymerization (ROP) with atom transfer radical polymerization (ATRP). First, a four-arm poly(?-caprolactone) (PCL) macroinitiator [(PCL-Br)₄] was prepared by the ROP of ?-CL catalyzed by stannous octoate at 110°C in the presence of pentaerythritol as the tetrafunctional initiator followed by esterification with 2-bromoisobutyryl bromide. The sequential ATRP of CCMA monomer was carried out by using the (PCL-Br)₄ tetrafunctional macroinitiator (MI) and in the presence of CuBr/2, 2′-bipyridyl system in DMF at 80°C with [(MI)]:[CuBr]:[bipyridyl] = 1:1:3 to yield block polymers with controlled molecular weights (M_n (NMR) = 10700 to 27300 g/mol) by varying block lengths and with moderately narrow polydispersities (M_w/M_n = 1.2–1.4). Block copolymers with different PCL: PCCMA copolymer composition such as 50:50, 70:30 and 74:26 were prepared with good yields (48-74%). All these block copolymers were well characterized by NMR, FTIR and GPC and tested their thermal properties by DSC and TGA.     

Mössbauer spectra of (Fe0.5Zn0.5)PS3 and its pyridine intercalate

Mössbauer spectra of (Fe_0.5Zn_0.5)PS₃, which is isomorphous with FePS₃, were measured at 300 and 80 K, and were compared with those of FePS₃. We succeeded in preparing (Fe_0.5Zn_0.5)PS₃ intercalated with pyridine. In the XRD pattern of the intercalate the diffraction peaks corresponding to (Fe_0.5Zn_0.5)PS₃ were completely missing, suggesting that the intercalation was completely performed with pyridine. The Mössbauer spectra were changed significantly by the intercalation suggesting the charge transfer from guest molecules to the host matrix. The replacement of iron by zinc has no influence on the electronic state of the iron atom, except for the magnetic interaction.     

Crystal Structures of [Ni(Phen)(i‐Bu2PS2)2] and [Ni(Phen)3](i‐Bu2PS2)2 Complexes and Interaction between Coordinated 1,10‐Phenanthroline Molecules

Single crystals of [Ni(Phen)(iBu₂PS₂)₂] (I) and [Ni(Phen)₃](iBu₂PS₂)₂ (III) compounds were grown, and their structures were determined by Xray diffraction analysis (CAD4 diffractometer, MoK radiation, 3336 F _hkl , R = 0.0373 for I and 2575 F _hkl for III). The crystals of complex I have a triclinic unit cell with the following parameters: a = 11.097(1) , b = 14.903(2) , c = 22.650(3); = 75.18(1)°, = 80.50(1)°, = 75.07(1)°, V = 3479.2(7)³, Z = 4, _calc = 1.255 g/cm³, and space group 1; the crystals of III have a monoclinic unit cell with the following parameters: a = 19.010(3), b = 15.481(1) , c = 17.940(3); = 97.58(1)°, V = 5233.5(12)³, Z = 4, _calc = 1.292 g/cm³, and space group C2/c. The structure of complex I is built from mononuclear molecules, and the structure of III, from [Ni(Phen)₃]²⁺ complex cations and i Bu₂PS₂ ^- outersphere anions. The NiN₂S₄ coordination polyhedra in the structure of I and NiN₆ in the structure of III are distorted octahedra. Based on structural data, the interaction between the coordinated Phen molecules of complexes I, [Ni(Phen)₂(iBu₂PS₂)](iBu₂PS₂) (II), and III is considered, as well as the packing modes of these complexes.     

Synthesis and photoluminescence of complexes Tm(L)(iso-Bu2PS2)2(NO3) (L = Phen, 2,2′-Bipy). Crystal structures of compounds [Ln(2,2′-Bipy)(iso-Bu2PS2)2(NO3)] · C6H6 (Ln = Tm, Tb)

Heteroligand complexes Tm(L)(iso-Bu₂PS₂)₂(NO₃) (L = 2,2′-Bipy (II), Phen (III)) are synthesized. According to the X-ray phase analysis data, complex III is isostructural to mononuclear compound [Dy(Phen)(iso-Bu₂PS₂)₂(NO₃)] including, according to the X-ray diffraction data, a coordination polyhedron DyN₂O₂S₄ (distorted dodecahedron). Single crystals of compounds [Ln(2,2′-Bipy)(iso-Bu₂PS₂)₂(NO₃)] · C₆H₆ (Ln = Tm (IV), Tb (V)) are obtained. An X-ray diffraction analysis shows that the crystal structures of these isostructural compounds are formed by molecules of mononuclear complexes [Ln(2,2′-Bipy)(iso-Bu₂PS₂)₂(NO₃) and uncoordinated C₆H₆ molecules. In complexes IV and V, the ligands [Ln(2,2′-Bipy)(iso-Bu₂PS ₂ ^? , and NO ₃ ^? are bidentate-cyclic. The coordination polyhedron LnN₂O₂S₄ is a distorted dodecahedron. Complexes II and III possess photoluminescence in the visible spectral range (λ_max = 478 and 477 nm, respectively).     

Thermal Stabilities of Attapulgite/Polystyrene (ATP/PS) Nanocomposites via Microwave‐Assisted Bulk Polymerization

Attapulgite/polystyrene (ATP/PS) nanocomposites with different contents of attapulgite nano‐needles organo‐modified, and cetyltrimethylammonium bromide (CTAB) were successfully prepared by the in situ bulk radical polymerization of styrene, under microwave irradiation. The transmission electron microscopy (TEM) results showed good dispersibility of the organo‐modified attapulgite nano‐needles in the polystyrene matrices. The thermogravimetric analysis (TGA) revealed that the thermal stability of the nanocomposite was enhanced with the increase of additional attapulgite nano‐needles.     

EFFECTS OF STYRENE-ETHYLENE/PROPYLENE DIBLOCK COPOLYMER (SEP) ON THE COMPATIBILIZATION OF PP/PS BLENDS

The effects of styrene-ethylene/propylene (SEP) diblock copolymer on the morphology and mechanical propertiesof polypropylene/polystyrene (PP/PS) blends were investigated. The results showed that SEP diblock copolymer, acting as acompatibilizer in PP/PS immiscible blends, can diminish the coalescence of the dispersed particles, reduce their averageparticle size, change their phase morphologies significantly, and increase the mechanical properties. It was found that SEP has better compatibilization effects on the PP/PS (20/80) blends.     

Synthesis and polymer structure of [Zn(4,4′-bipy){(i-PrO)2PS2}2]n and thermal properties of ZnL{(i-PrO)2PS2}2 (L = phen, 2,2′-bipy, 4,4′-bipy)

A new mixed-ligand complex, Zn(4,4′-bipy){(i-PrO)₂PS₂}₂, was synthesized. Single crystals were grown,and the structure of the complex was determined by X-ray diffraction (CAD-4 diffractometer, MoK_α radiation, 14807 F_hkl, R =0.0391. The crystals are monoclinic with unit cell dimensions a-17.569(2), b = 26.253(5), c = 27.915(3) Å, ß =100.70(1)°, V = 12652(3) ų, Z = 16, d_valc = 1.361 g/cm³, space group P2₁/n. The structure is formed from infinite zigzag polymer chains stretched along the a axis. The coordination polyhedron of the Zn atom is a distorted tetrahedron formed by two S atoms of two monodentate diisopropyldithiophosphate ligands and two N atoms of two bridging bidentate 4,4′-bipy molecules. When heated in vacuum, the compounds ZnL{(i-PrO)₂PS₂}₂ (L) =phen, 2,2′-bipy, 4,4′-bipy are volatile.