Structure and phase transitions in poly[bis-(2,2,3,3-tetrafluoropropoxy) phosphazene]

The structure and phase transitions in poly[bis-(2,2,3,3-tetrafluoropropoxy)phosphazene] have been studied by differential scanning calorimetry (DSC) and x-ray diffraction. Two crystalline phases and one mesomorphic phase are found, denoted I, II, and III, respectively. These phases convert reversibly one into the other on heating and cooling. The Phase I–Phase II transition occurs in a temperature range from 5 to 30°C whereas the Phase II mesophase (Phase III) transition proceeds above 80°C. Heats of transitions are measured to be about 29.0 J/g and 3.6 J/g, respectively. Crystalline Phase I is characterized by a monoclinic unit cell with the parameters: α = 24.4 Å, b = 9.96 Å, c = 4.96 Å, γ = 123°. The axes of both chains, traversing the unit cell, are directed along the “c” axis, the main chains having cis-trans conformation. Phase I is the common crystalline structure for the main chain and side chains. The structure of Phase II is controlled mainly by packing of the side chains. Transition of Phase II into mesomorphic Phase III is accompanied with distortion of packing of the side chains. Only regular packing of the main chains of macromolecules in the plane perpendicular to their axes exists in Phase III. Mesomorphic phase III is stable up to the degradation temperature of the polymer. A significant effect of stress on the Phase II–III transition in oriented samples was found.     

β-萘酚取代聚磷腈的合成与表征

The method of preparing N-dichlorophosphoryl-P-trichloromonophosphazene as monomer from PCl5 and(NH4)2 SO4 in 1, 1, 2, 2-tetrachloroethane was investigated. Polydichlorophosphazene can be obtained from the polycondensation of this monomer and poly (β-naphthyloxy) phosphazen (I) was prepared from polydichlorophosphazene and sodium β-naphthyloxy.At the same time, the IR, 31P NMRof the title polymers were determined.The glass transition and viscous flow temperatures determined by TBAare-83℃ and 19℃respectively. Decomposition temperature measured by TGis 338℃.The Mn of Iestimated by VPOis 4110.     

The thermal transition behavior of poly(bis(p-flourophenoxy)phosphazene)

The thermal transition behavior of poly(bis(p-fluorophenoxy)phosphazene) was studied as a representative aryloxy-substituted poly(organophosphazene) using X-ray diffraction, differential thermal analysis and density measurements. The crystal structure of-form contained in as-cast film had marked paracrystalline disorder. The crystal phase transformed into the mesophase atT(1) (110 140 °C). The structure of the-form observed in the mesophase was a representative hexagonal-packing of macromolecular chains which rotate around the chain axes. When the mesophase was cooled to room temperature, a more ordered crystal phase of the-form could appear. The most ordered crystal structure of the-form has a monoclinic unit cell with the following lattice parameters: a=18.9, b=13.2, c=4.90 Å, and=77°. The chain conformation is nearly planar cis-trans, which has been observed commonly in poly(organophosphazenes). The macroscopic deformation of the film sample was also examined, taking into account the microscopic deformation of the lamellar crystal due to the crystal-mesophase transition.     

Poly(organophosphazenes)--unusual new high polymers.

An inorganic-backbone high polymer system based on alternating phosphorus and nitrogen atoms promises to solve many of the problems hitherto associated with conventional organic polymers. The chemistry, structure, biomedical, and technological aspects of these polymers are reviewed.     

Molekül- und Kristallstruktur des Dimeren Magnesium-bis[bis(trimethylsilyl)amids]

Molecular and Crystal Structure of the dimeric Magnesium bis[bis(trimethylsilyl)-amide] The magnesium bis[bis(trimethylsilyl)amide] crystallizes as a dimeric molecule in the space group C2/c with {a = 1821.0(4); b = 1494.4(4); c = 1859.6(6) pm; β = 121.10(2)°; Z = 4 dimers}. The cyclic planar Mg₂N₂ moiety shows endocyclic NMgN angles of 95.8°. The bond lengths within this ring system to the four-coordinate, bridging nitrogen atoms N^b are 215 pm, whereas the distances between the magnesium atom and the terminal, three-coordinate nitrogen atom N^t display values of approximately 198 pm. These different coordination numbers of the nitrogen atoms affect the NSi bond length (N^tSi 171, N^bSi 177 pm).     

Facile synthesis and characterization of novel benzo-fused macrocyclic dicarbonitriles and pyrazolo-fused macrocycles containing thiazole subunits

Abstract

Novel bis[2-(thiazol-2-yl)acetonitriles], linked to aliphatic cores via ethers, were prepared by the reaction of the appropriate bis(2-bromoethan-1-one) with 2-cyanothioacetamide in dioxane at reflux. Bis[2-(thiazol-2-yl)acetonitriles] were taken as key intermediates for the preparation of a new class of macrocyclic dicarbonitriles bearing two thiazole units and containing two O₂-donor sets and fused with two benzene units. The target macrocyclic dicarbonitriles were prepared by the cyclocondensation of bis[2-(thiazol-2-yl)acetonitriles] with the appropriate bis(aldehydes) in N,N-dimethylformamide in the presence of piperidine at reflux. Moreover, a new class of pyrazolo-fused macrocycles containing thiazole subunits were prepared by the reaction of macrocyclic dicarbonitriles with hydrazine hydrate in ethanol at reflux. The structures of the novel macrocycles bearing thiazole subunits were elucidated by considering their elemental analyses as well as their IR, mass, ¹H NMR and ¹³C NMR spectral data.     

Synthesis and self‐association behavior of poly[bis(2‐(2‐methoxyethoxy)ethoxy)phosphazene]‐b‐poly(propyleneglycol) triblock copolymers

Amphilic triblock copolymers with varying ratios of hydrophilic poly[bis (methoxyethoxyethoxy)phosphazene] (MEEP) and relatively hydrophobic poly(propylene glycol) (PPG) blocks were synthesized via the controlled cationic‐induced living polymerization of a phosphoranimine (Cl₃P?NSiMe₃) at ambient temperature. A PPG block can function as either a classical hydrophobic block or a less hydrophobic component by varying the nature of a phosphazene block. The aqueous phase behavior of MEEP‐PPG‐MEEP block copolymers was investigated using fluorescence techniques, TEM, and dynamic light scattering (DLS). The critical micelle concentrations (cmcs) of MEEP‐PPG‐MEEP block copolymers were determined to be in the range of 3.7–16.8 mg/L. The mean diameters of MEEP‐PPG‐MEEP polymeric micelles, measured by DLS, were between 31 and 44 nm. The equilibrium constants of pyrene in these micelles ranged from 4.7 × 10⁴ to 9.6 × 10⁴. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 692–699, 2009     

Synthesis and characterization of aromatic cyclolinear phosphazene polyetherketones containing bis‐Spiro‐substituted cyclotriphosphazene unit

A novel monomer, 2,2‐bis‐(4′‐fluorobenzoylphenoxy)‐4,4,6,6‐bis[spiro‐(2′,2″‐dioxy‐1′, 1′‐biphenylyl)] cyclotriphosphazene, was synthesized and polymerized with 4,4′‐difluorobenzophenone as a comonomer and 4,4′‐isopropylidenediphenol or 4,4′‐(hexafluoroisopropylidene) diphenol in N,N‐dimethylacetamide at 162 °C for 4 h to give two series of aromatic cyclolinear phosphazene polyetherketones containing bis‐spiro‐substituted cyclotriphosphazene groups. The structure of the monomer was confirmed by ¹H, ¹³C, and ³¹P NMR. The effect of the incorporation of the bis‐spiro‐substituted cyclotriphosphazene group on the thermal properties of these polymers was investigated by DSC and thermogravimetric analysis. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2993–2997, 2001     

聚[(六氟异丙氧基)_(2-x)(三氟乙氧基)_x]磷腈合成和气体分离性能研究

合成制备了聚磷腈类高分子——聚[(六氟异丙氧基)2-x(三氟乙氧基)x]磷腈,并通过NMR、FTIR、XRD、GPC、DSC等测试手段对聚合物进行了结构表征和性能测试,通过压力法透气性能测定仪测定了聚合物膜对N2、O2、CH4、CO2、He、H2等气体的透过性能.结果表明,三氟乙氧基的竞争取代能力较六氟异丙氧基稍强;得到x值分别为1.64、1.72和1.81的3种聚合物;其玻璃化温度Tg为-20.21℃、-42.83℃和-43.41℃;重均分子量为5.06×105、1.49×105和2.69×105;两种取代基比例适中时显示出较高的气体透过性能,渗透系数PN2=20barrer,PCO2=124barrer,PHe=85barrer;CO2/CH4和He/CH4的选择系数达到11.5和4.8,在天然气的净化和回收He中显示了潜力;H2/N2的选择系数达到6,而PH2=43barrer,在合成NH3尾气中回收H2存在发展前景。     

Bis(trimethylsilyl)amide und -methanide des Yttriums — Molekülstrukturen von Tris(diethylether-O)lithium-(μ-chloro)-tris[bis(trimethylsilyl) methyl]yttriat,solvensfreiem Yttrium-tris[bis(trimethylsilyl)amid] sowie dem Bis(benzonitril)-Komplex

Bis(trimethylsilyl)amides and -methanides of Yttrium — Molecular Structures of Tris(diethylether-O)lithium-(μ-chloro)-tris[bis(trimethylsilyl)methyl]yttriate, solvent-free Yttrium Tris[bis(trimethylsilyl)amide] as well as the Bis(benzonitrile) Complex The reaction of yttrium(III) chloride with the three-fold molar amount of LiE(SiMe₃)₂ (E = N, CH) yields the corresponding yttrium derivatives. Yttrium tris-[bis(trimethylsilyl)amide] crystallizes in the space group P3 1c with a = 1 636,3(2), c = 849,3(2) pm, Z = 2. The yttrium atom is surrounded trigonal pyramidal by three nitrogen atoms with Y? N-bond lengths of 222 pm. Benzene molecules are incorporated parallel to the c-axes. The compound with E = CH crystallizes as a (Et₂O)₃LiCl-adduct in the monoclinic space group P2₁/n with a = 1 111,8(2), b = 1 865,2(6), c = 2 598,3(9) pm, β = 97,41(3)° and Z = 4. The reaction of yttrium tris[bis(trimethylsilyl)amide] with benzonitrile yields the bis(benzonitrile) complex, which crystallizes in the triclinic space group P1 with a = 1 173,7(2), b = 1 210,3(2), c = 1 912,4(3) pm, α = 94,37(1), β = 103,39(1), γ = 117,24(1)° and Z = 2. The amido ligands are in equatorial, the benzonitrile molecules in axial positions.     

聚[(四氟丙氧基)2-x(三氟乙氧基)x]膦腈合成和气体分离性能研究

以六氯环三聚磷腈为原料通过真空热开环聚合制得线型聚二氯磷腈(PDCP),再通过对PDCP进行亲核取代合成制备了新的聚膦腈类高分子--聚[(四氟丙氧基)2-x(三氟乙氧基).]膦腈,聚合物经过四氢呋喃-苯反复溶解-沉淀得到纯化产物.通过31P-NMR、1H-NMR和FTIR对其结构进行了表征;DSC法测定其玻璃化转变温度...     

静电喷雾法制备聚膦腈微球

用静电喷雾法制备了粒径窄分布的甘氨酸乙酯-苯丙氨酸乙酯取代聚膦腈的微球.主要探讨了溶剂、溶液浓度、流速、喷射电压及接收距离对微球形貌和粒径的影响.微球的表面形貌与溶剂性质和聚合物溶液浓度密切相关,微球粒径受聚合物溶液流速的影响比较显著,随流速增大粒径呈单调上升趋势.结果显示对于[η]=0.1 dL/g的(甘氨酸乙酯)0.3(苯丙氨酸乙酯)0.7取代聚膦腈,以0.25 g/mL的四氢呋喃溶液进行静电喷雾,可获得粒径分布窄(1~2μm)且近球形的微粒,其工艺条件可进一步用于载药聚膦腈微球的制备和控制释放研究.     

胆固醇修饰的低分子量聚乙烯亚胺接枝化聚[L-天冬酰胺-co-L-赖氨酸]作为基因载体的性能研究

通过将低分子量的聚乙烯亚胺(PEI600)及其胆固醇衍生物与聚(L-天冬酰胺-co-L-赖氨酸)(PSL)进行开环反应, 合成了一类新型的肿瘤靶向基因载体, 研究了这类载体与DNA形成复合物的性质以及介导绿色荧光蛋白质粒pEGFP-C1转染不同细胞的性能. 结果表明, 在复合质量比大于5∶1时, 各载体均能与DNA形成结构稳定的复合物. 同时转染实验结果证明, 通过在侧链引入一定数目的胆固醇, 可以明显提高载体对于癌细胞HepG2和Hela的转染效率. 这类新型的载体具有良好的细胞相容性、较高的转染效率以及易于进行靶向修饰等特点, 在基因治疗研究领域中将具有较好的潜在应用价值.     

Polymers containing phenylquinoxaline rings

The synthesis and properties of poly(phenylquinoxalines) containing hexafluoroisopropylidene or silylene units in the backbone are described. The polymers have been prepared by polycondensation of aromatic diamines containing preformed phenylquinoxaline rings with a dianhydride or diacid chlorides containing hexafluoroisopropylidene groups, or with a dianhydride or diacid chlorides containing silylene units. The solubility, thermal stability, film forming ability, and electric insulating, mechanical, and electroluminescent properties of the thin films are discussed and compared with those of related heterocyclic polymers. Potential applications of poly(phenylquinoxalines) are outlined.Based on the report presented at the International Conference Modern Trends in Organoelement and Polymer Chemistry dedicated to the 50th anniversary of the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences (Moscow, May 30–June 4, 2004).Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1739–1748, September, 2004.     

Polystyrene bis[N-(2-pyridyl) sulfonamide] palladium(II): Synthesis,characterization as a catalyst for coupling reactions

The [N-(2-pyridyl)] para-styrene sulfonamide (PSS) was prepared as a monomer, from the reaction of para-styrene sulfonyl chloride and 2-amino pyridine in the presence of potassium hydroxide solution 0.5 M as a base, and CH₃Cl. Polystyrene [N-(2-pyridyl) sulfonamide] (PPSS) was synthesized from the polymerization of [N-(2-pyridyl)] para-styrene sulfonamide (PSS). The Polystyrene bis [N-(2-pyridyl) sulfonamide] palladium (II) as a polymer- supporting palladium complex was also prepared from the reaction of PdCl₂ (CH₃CN)₂ with PPSS in the presence of KOH 0.5 M. Polystyrene bis [N-(2-pyridyl) sulfonamide] palladium (II) is produced as a novel heterogeneous catalyst for coupling reactions for C-C bond formation. This method includes higher yield and has an easier work-up procedure. The structures of the monomer, polymer and its Pd complex were confirmed by using FT-IR and ¹H-NMR spectroscopy. Elemental analysis of Pd by inductively coupled plasma (ICP) technique and hot filtration test showed loading of the metal into solution from the catalyst The heterogeneous catalyst was recycled without any loss in its properties.     

Synthesis and Crystal Structure of Bis[a-chloro-(o-chloro-benzylidene)] Hydrazine

1 INTRODUCTION The azine derivatives are useful compounds because of their special properties. On the one hand, the azines and ,-dichloro-azines are very impor- tant intermediates[1, 2] for synthesizing s-tetrazines which have some peculiar properties, s…     

Synthesis of novel aromatic ether polymers containing perfluorocyclobutyl and triazole units via click chemistry

The synthesis and characterization of a novel class of linear aromatic ether polymers containing perfluorocyclobutyl and triazole unites is described. These polymers were prepared from the click chemistry (the copper-catalyzed Huisgen's 1,3-dipolar cycloaddition) of new monomer 1,2-bis(4-azidomethylphenoxy) perfluorocyclobutane and bisethynyl compounds.     

溶剂性质对两亲性聚肽静电纺丝的影响

通过对聚(γ-苄基L-谷氨酸酯)(PBLG)的亲水改性制备了两亲性聚(γ-苄基L-谷氨酸酯-co-羟乙谷酰胺)无规共聚肽(PBHG)用于静电纺丝制备超细纤维.通过傅里叶变换红外光谱、核磁共振氢谱表征了聚合物结构.通过测定溶液表面张力、黏度、电导率及扫描电镜观察纤维形貌考察了不同溶剂及PBHG浓度对纺丝溶液性质及电纺纤维的影响.通过水浸实验及MTT法评价了电纺纤维膜的亲水性及细胞相容性.研究发现在三氯甲烷(TCM)和四氢呋喃(THF)中PBHG采取α-螺旋构象,刚性分子链自取向排列,可获得直径为微米或亚微米的电纺纤维.以TCM为溶剂时,因溶液表面张力大、导电率低导致纤维品质较差,而以THF为溶剂可获得表面光洁、尺寸均匀的电纺纤维.当溶剂为三氟乙酸(TFA)时,PBHG采取无规线团构象,柔性分子链彼此缠结,同时溶液表面张力小、黏度低、电导率高,可获得纳米电纺纤维.但因TFA挥发性相对较差,易造成纤维粘连.将TFA与TCM复配后作为溶剂可改善纤维粘连问题.与PBLG电纺纤维相比,改性后的PBHG电纺纤维的亲水性得到了改善,可在水中保持纤维骨架而无需交联,并表现出良好的细胞相容性,能促进细胞在电纺纤维膜上的增殖.     

Anti-biofouling by degradation of polymers

Copolymers of methyl methacrylate (MMA) and acrylate terminated poly(ethylene oxide-co-ethylene carbonate)(PEOC) macromonomer (PEOCA) were synthesized,and the degradation of the polymers was investigated by use of quartz crystal microbalance with dissipation (QCM-D).It is shown that the polymeric su     

Hemoglobin binding from human blood hemolysate with poly(glycidyl methacrylate) beads

Metal-chelating affinity beads have attracted increasing interest in recent years for protein purification. In this study, iminodiacetic acid (IDA) was covalently attached to the poly(glycidyl methacrylate) [PGMA] beads (1.6 μm in diameter). Cu(2+) ions were chelated via IDA groups on PGMA beads for affinity binding of hemoglobin (Hb) from human blood hemolysate. The PGMA beads were characterized by scanning electron microscopy (SEM). The PGMA-Cu(2+) beads (628 μmol/g) were used in the Hb binding-elution studies. The effects of Hb concentration, pH and temperature on the binding efficiency of PGMA-Cu(2+) beads were performed in a batch system. Non-specific binding of Hb to PGMA beads in the absence of Cu(2+) ions was very low (0.39 mg/g). The maximum Hb binding was 130.3 mg/g. The equilibrium Hb binding increased with increasing temperature. The negative change in Gibbs free energy (ΔG°<0) indicated that the binding of Hb on the PGMA-Cu(2+) beads was a thermodynamically favorable process. The ΔS and ΔH values were 102.2 J/mol K and -2.02 kJ/mol, respectively. Significant amount of the bound Hb (up to 95.8%) was eluted in the elution medium containing 1.0 M NaCl in 1 h. The binding followed Langmuir isotherm model with monolayer binding capacity of 80.3-135.7 mg/g. Consecutive binding-elution experiments showed that the PGMA-Cu(2+) beads can be reused almost without any loss in the Hb binding capacity. To test the efficiency of Hb depletion from blood hemolysate, eluted portion was analyzed by fast protein liquid chromatography. The depletion efficiency for Hb was above 97.5%. This study determined that the PGMA-Cu(2+) beads had a superior binding capacity for Hb compared to the other carriers within this study.