Synthesis of Biological Activities of Phosphorus-Containing Polycationic Strings

Abstract

Several series of phosphoruscontaining polycationic strings have been prepared. These include those in which quaternary phosphonium sites are located at regular intervals along a linear chain of defined length (“Strings”), and those in which the cationic phosphonium, sites are in linkages arrayed in branching arms about a cenhal focus unit (“baloons”). Polyphosphonium “balloon” arrays have been attached to a polystyrene backbone prowding a mataial which serves as an anionic exchange resin. PolyCationic strings have been prepared in which phosphorus is present a3 phosphine oxide functidties and the cationic sites are quatanary ammonium sites anayed at regular intervals along a linear chain of defined length. Several of the resultant materials have demonshated sigruficant antibaaaial activity. Interactions of the polycationic species with the anionic gmove region of double stranded DNA have been investigated.     

Preparation et caracterisation des polymeres tete-a-tete—VI. Proprietes physicochimiques du polystyrene tete-a-tete en solution diluee. Comparaison avec des polystyrenes de structure differente

The dilute solution properties of head-to-head polystyrene are reported. Determination of the “θ” temperature in cyclohexane has been made and compared with the “θ” temperature of the head-to-tail polystyrene (polyprotostyrene and poly-deuteriostyrene). The viscometric behaviour in a good solvent has been also examined and compared with the properties of head-to-tail polystyrenes (atactic, isotactic and deuterated).     

Molecular weight distributions in radiation-induced polymerization. VII. γ-ray-induced polymerization of “wet” styrene in the solid state

In the present paper kinetic and molecular weight distribution results are reported for the γ-ray-initiated polymerization of styrene in the solid state. “In-source” polymerization over the temperature range ?35°C to ?55°C and post-polymerization at ?35°C have been investigated for “wet” styrene samples (water concentration ≈ 10^?3 mole/l.). An interesting feature of the solid-state polymerization of styrene is the bimodal nature of the molecular weight distribution. On a qualitative basis the results resemble those obtained previously for the polymerization of rigorously dried (“dry”) styrene. However, there are noticeable differences on a quantitative basis resulting from the considerable difference in the water content between wet and dry samples. On the basis of these studies, the kinetic and molecular weight distribution data have been interpreted as being indicative of polymerization occurring simultaneously via free-radical and cationic mechanisms.     

Molecular interactions in polystyrene cosolvent systems

Studied here are miscible binary cosolvents for polystyrene, for which polystyrene is insoluble in either of the individual solvents. Polymer-solvent interactions in solutions of atactic polystyrene in acetone/diethyl ether and in methylcyclopentane (MCP)/acetone binary cosolvents have been investigated using nuclear magnetic resonance (NMR) spectroscopy. Polystyrene ¹³C chemical shifts were measured as a function of miscible binary solvent compositions and temperature. The NMR data were used to calculate “association constants” as a measure of specific interactions of the solvent components with all sites on the polymer. In mixtures of acetone and diethyl ether, ¹³C-NMR indicates a weak interaction between the polystyrene phenyl ring and the diethylether solvent component. In the polystyrene/MCP/acetone system, present NMR data reveal no preferential interactions. Additional NMR measurements were performed on polystyrene in mixtures of CCl₄/acetone. From these results, it is concluded that although preferential polymer-solvent interactions are present in some cosolvent systems, they are not a prerequisite for such behavior.     

Dynamic mechanical thermal and infrared analyses of polyacrylonitrile “electrografted” onto a metal

Polyacrylonitrile (PAN) films have been “grafted” onto copper electrodes by cathodic polarization and analyzed by infrared spectroscopy and dynamic mechanical thermal analysis (DMTA). The dynamic mechanical response shows two or three transitions depending on the film thickness and the potential deposition. The viscoelastic properties of “ungrafted” PAN films, e.g., solvent cast films of commercially available PAN, are deeply different from those of “electrografted” films. The experimental data support that “ungrafted” chains are paracrystalline in contrast to the “grafted” ones which are essentially amorphous. Moreover, the irreversible transformation of the “grafted” PAN chains observed beyond 225°C is confirmed by Fourier transform infrared (FTIR) analysis and ascribed to an intramolecular cyclization of PAN into polyimine. This reaction occurs rapidly and at a comparatively low temperature with respect to “ungrafted” PAN, which suggests that the “grafted” chain configuration might be predominantly isotactic. The isotacticity and the amorphous structure appear to decrease as the thickness of the PAN film is increased. Literature data and the herein reported observations would suggest a dependence of the amorphous structure of PAN on the chain isotacticity. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 543–553, 1998     

非MAO的茂钛均相催化体系催化苯乙烯间规聚合——[Cp~*TiMe_3]/[Ph_3C]~+[B(C_6F_5)_4]~-催化体系

非ＭＡＯ的茂钛均相催化体系催化苯乙烯间规聚合———［ＣｐＴｉＭｅ３］／［Ｐｈ３Ｃ］＋［Ｂ（Ｃ６Ｆ５）４］－催化体系许光学林尚安（中山大学高分子研究所广州５１０２７５）关键词茂钛络合物，茂金属催化剂，苯乙烯，间规聚苯乙烯间规聚苯乙烯（ｓＰＳ）由于具...     

Viscoelastic properties of entangled polymers. II. The interchain–intrachain entanglement model

Our earlier model of entangled chain dynamics represented the elastic effects at entanglement points as a coupling with the surrounding medium, which was propagated weakly to every other entanglement site on the parent chain. In this way, a great variety of linear viscoelastic phenomena could be successfully predicted, with the only significant deficiency being a quantitative failure in curve fitting the local minimum in dynamic loss modulus G″(ω). Here we introduce the “intrachain entanglement,” or the “internal entanglement,” in which the parent chain entangles directly with itself. Elastic forces between pairs of internal entanglements are assumed to be stronger than those with the medium (“external entanglement”). Predictions of the new model are compared with rheological data on monodisperse polystyrene. Good agreement is obtained between theory and experiment, including G″(ω).     

Magnetic circular dichroism studies of polystyrene solutions

The magnetic circular dichroism (MCD) spectra of “atactic” and isotactic polystyrene solutions have been found to be sensitive to configurational and conformational differences. The ratio of B terms for “atactic” polystyrene (predominantly syndiotactic) to that of cumene was found to pass through a minimum as the coil expanded in various solvents. The ratio of dipole strengths D also passed through a minimum. For isotactic polystyrene and cumene the ratio of B terms increased with increasing coil size in the range of solvents utilized. The ratio of B terms of isotactic polystyrene over atactic polystyrene was found to go through a maximum as the coil expanded whereas the ratio of dipole strengths was found to continuously decrease. These results have been interpreted on the basis of the change in short range and long range orientation and interaction distances between chromophores during coil expansion. It is concluded that the microscopic conformation of isotactic and atactic polystyrene are very different in very good solvents. The B/D ratio for cumene was found generally to decrease with increasing solvent power.     

Polycations. II. Chiral ammonium dendrimer synthesis

The preparation and investigation of chiral cationic dendrimers is described. In these species, cationic sites are provided by quaternary ammonium ion centers derived from the dinitrogen compound 1,4-diazabicyclo[2.2.2]octane (dabco). Stereogenic sites within the dendrimer structures are provided by derivitization of the readily available (S)-1,2,4-butanetriol. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9: 485–494, 1998     

Grafting of living poly(ethylene oxide) onto polystyrene via aromatic nucleophilic displacement of activated nitro groups

Polystyrene of M?_ω = 2.2 × 10⁴ was alkylated with 4-nitrophthalimidomethyl groups as grafting sites. Several backbone polymers with various degrees of grafting sites (G = 2–100%) were prepared and characterized by elemental analysis, IR, ¹H- and ¹³C-NMR, and viscosity measurements. “Living” poly(ethylene oxide) with narrow molecular-weight distribution was prepared in the presence of 15-crown-5, and grafted onto the 4-nitrophthalimidomethylated polystyrene. The nitro displacement reaction was fast and the grafting yield was quantitative (100%). The graft copolymers are highly soluble in water and in organic solvents. The intrinsic viscosities of the graft copolymers are higher than those of the backbone polymers. The intrinsic viscosities show an initial increase followed by a decrease as the degree of grafting increase.     

Crystallization kinetics of isotactic polystyrene. II. Influence of thermal history on number of nuclei

The influence of various thermal pretreatments on the nucleation of isotactic polystyrene has been studied quantitatively by dilatometry. A distinction can be made between nuclei still present above the melting point (“resistant” nuclei) and nuclei created by severe supercooling (“induced” nuclei). The number of spherulites formed has been determined for different combinations of supercooling and crystallization temperatures. The results are interpreted in a satisfactory manner by assuming that in severe supercooling induced nuclei are created, which may grow into effective nuclei at higher temperatures. The crystallization of a severely supercooled polymer is completely governed by these induced nuclei, because they outnumber the resistant nuclei by some orders of magnitude. The number of induced nuclei can be decreased by purifying the polymer (removing catalyst residues). When cooled polymer is heated to temperatures just above the melting point, the induced nuclei are destroyed (“reversible melting”), so that only the resistant nuclei, which are few in number, remain. These resistant nuclei govern the crystallization behavior of a polymer which has not previously been cooled. Their number decreases on heating to temperatures far above the melting point.     

Volume Effect or Paddle-Wheel Mechanism—Fast Alkali-Metal Ionic Conduction in Solids with Rotationally Disordered Complex Anions

Transport phenomena in the solid state are of equal importance in basic research and practice. In the past two decades particular interest has been directed towards so-called “fast” or “super” ionic conductors because of their attractive potential applications. We have synthesized highly conductive alkali-metal ionic conductors based on ionic crystals in which, on the one hand, high concentrations of the charge carriers can be realized by doping (point defects in the cation substructure) and, on the other, the activation energy of the interchange of sites is decreased by translationally fixed but rotationally mobile complex anions. Mixed crystals with Na₃PO₄ or Na₃AlF₆ structures have proven especially suitable in this connection. With the object of establishing a broader experimental foundation for clarifying the controversially discussed question of whether the higher free transport volume or the rotational motion of the anions is responsible for the high cation mobility in these rotary phases we have systematically varied the type of anions and concentration of defects and monitored the resulting changes in conductivity. Although the macroscopical characteristics investigated are not suitable for explaining mechanisms in detail at the atomic level, the results afford clear support for the assumption of a “paddle wheel mechanism”; but also effects of the enlarged transport volume are not to be disputed. Both these effects enhancing the cationic conductivity are concomitantly operative in amounts varying from system to system; they cannot be totally separated from each other. Seen in this light, the alternative, “volume effect” or “paddle wheel mechanism,” is not as sharply defined as was previously discussed.     

Thermisch stimulierte Lumineszenzerscheinungen. I Einfluß der Vorbehandlung von Kupferstaub und das Phänomen „Kontaktgedächtnis”︁

Thermally Stimulated Luminescence Phenomena. I. Influence of Pretreatment of Copper Dust and the Phenomenon “Contact Memory” The thermally stimulated luminescence of so-called “copper dust” is strongly influenced by its pretreatment. Samples which have been cooled prior to measurement show lower energies and those which have been mechanically treated, irradiated or heated, show higher thermoluminescence energies than samples which have been stored normally. After removal of the samples from the metallic carrier and subsequent heating of the latter, the thermoluminescence energies are proportional to those found for the sample measured immediately before. This phenomenon is considered as “contact memory”. All results are interpreted according to the concept of the hierarchic order.     

Unusual random walks

For most structures (molecules, graphs, lattices) a count of random walks for nonequivalent sites will give different numbers, particularly for walks of many steps. Occasionally one finds the same count of walks for nonequivalent sites. These have been termed “unusual walks” and have been closely examined in the case of trivalent graphs. While it remains to be understood what structural factors are critical, some regularities have been observed and are discussed. Unusual walks within a single structure signal “isospectural” points in a graph. A number of structures possessing unusual walks have been displayed, and a few constructive steps which do not alter the “unusual” characteristics of selected vertices have been indicated.     

Polymérisation en milieu précipitant du styrène en solution dans différents alcools

Earlier studies from this laboratory on the polymerizations of acrylic acid and acrylonitrile under precipitating conditions have shown that the auto-acceleration is not caused by non-stationary conditions resulting from the precipitation of growing chains (“occlusion effect”) but by a “matrix effect”, an oriented association complex between the monomer and the polymer formed in the early stages of the reaction leading to assisted propagation. In the present work, a non-polar monomer-polymer system was selected in which molecular associations are unlikely. It was found that when polystyrene precipitates as a fine powder (in diluted monomer solutions in alcohols) auto-acceleration is observed but its extent drops with increasing rate of initiation and increasing temperature. Such situations do not arise in polymerizing systems in which a “matrix effect” operates. The study of the post-polymerization and of the swelling of polystyrene in styrene (10-propanol (90) mixtures) led to the conclusion that polystyrene in equilibrium with this mixture exhibits a glass transition temperature at ca 50°. The various results obtained in this study conform with the assumption of an occlusion effect. The growing chains being buried in the precipitated polymer, chain termination is severely restricted and becomes the determining step in the polymerization.     

Synthesis of ring-shaped macromolecules

Ring-shaped macromolecules have been synthesized by the reaction of a bifunctional “living” polystyrene with a stoichiometric amount of dibromo-p-xylene, at very low concentration. The reaction is carried out step by step, leading both to the expected cyclic polymer and to a “polycondensate”. Fractionatal precipitation and one-step fractionation lead to well defined macrocycles of known size.     

Two-dimensional near-infrared correlation spectroscopy studies of polymer blends I: Composition-dependent spectral variations of blends of atactic polystyrene and poly[2,6-dimethyl-1,4-phenylene ether]

Generalized two-dimensional (2D) near-infrared (NIR) correlation spectroscopy has been applied to study the conformational changes and molecular interactions in blends of atactic polystyrene (PS) and poly[2,6-dimethyl-1,4-phenylene ether] (PPE). NIR diffuse reflectance spectra have been measured for PS, PPE and their blends of different compositions, i.e., PS/PPE=90/10, 70/30, 50/50, 30/70, 10/90. The 2D synchronous correlation analysis of these composition-dependent NIR spectral variations separates the bands of PS from those of PPE. The 2D asynchronous analysis identifies spectral features indicative of the conformational changes or the specific interaction of PS and PPE. It can also detect “blend bands” whose origin is attributed to the formation of the polymer blends. Two “blend bands” of PS are identified at 6887 and 4836 cm⁻¹, and three “blend bands” of PPE are observed at 5752, 5679 and 4647 cm⁻¹. These “blend bands” are due to vibrations of the aromatic rings of PS or PPE and of the CH₃ of PPE. Thus, not only the aromatic rings of PS and PPE but also the CH3 groups of PPE play important roles in the formation of the blends.     

Cyclic macromolecules. Synthesis and characterization of ring-shaped polystyrenes

A method has been developed to synthesize cyclic polystyrene molecules, by reacting bifunctional “living” polystyrene with α,α′ dibromo-p-xylene. The ability of the method to yield cyclic polymers over a molecular weight range from 7000 to 250,000 has been thoroughly investigated and discussed. Characterization of the cyclic macromolecules with respect to linear homologues of the same molecular weight has been performed by means of viscometry. The effect of cyclization tends to decrease as the molecular weight increases.     

Methods in high resolution gas chromatography. Two-dimensional techniques

Basic methodology to effect the separation of complex samples by gas chromatography is discussed from an experimental point of view. Several possibilities are presented which are commonly used to enhance the information content of a gas chromatographic run. These include incorporation of more than one set of retention data, multiple detectors, and special column switching techniques. These and other techniques have sometimes been labeled “multidimensional” in the literature. An attempt is made to define the term “two-dimensional chromatography”. The review is divided into sections which point out the different directions which have been taken to deconvolute chromatographically unresolved components. Particular emphasis is placed on technology which is capable of dealing with samples of extreme complexity, and instrumentation for trace- and ultratrace analysis is dicussed with specific examples. The future of two-dimensional techniques in gas chromatography is looked into.     

Molecular orbital theory of the hydrogen bond. 24. Ground-state water–uracil complexes

Ab initio SCF calculations with the STO -3G basis set have been performed to investigate the structural, energetic, and electronic properties of mixed water–uracil dimers formed at the six hydrogen-bonding sites in the uracil molecular plane. Hydrogen-bond formation at three of the carbonyl oxygen sites leads to cyclic structures in which a water molecule bridges N₁? H and O₂, N₃? H and O₂, and N₃? H and O₄. Open structures form at O₄, N₁? H, and N₃? H. The two most stable structures, with energies of 9.9 and 9.7 kcal/mole, respectively, are the open structure at N₁? H and the cyclic one at N₁? H and O₂. These two are easily interconverted, and may be regarded as corresponding to just one “wobble” dimer. At 1 kcal/mole higher in energy is another “wobble” dimer consisting of an open structure at N₃? H and a cyclic structure at N₃? H and O₄. The third cyclic structure at N₃? H and O₂ collapses to the “wobble” dimer at N₃? H and O₄. The two “wobble” dimers are significantly more stable than the open dimer formed at O₄, which has a stabilization energy of 5.4 kcal/mole. Uracil is a stronger proton donor to water through N₁? H than N₃? H, owing to a more favorable molecular dipole moment alignment when association occurs through H₁. Hydration of uracil by additional water molecules has also been investigated. Dimer stabilization energies and hydrogen-bond energies are nearly additive in most 2:1 water:uracil structures. There are three stable “wobble” trimers, which have stabilization energies that vary from 7 to 9 kcal/mole per water molecule. Hydrogen-bond strengths are slightly enhanced in 3:1 water:uracil structures, but the cooperative effect in hydrogen bonding is still relatively small. The single stable water–uracil tetramer is a “wobble” tetramer, with two water molecules which are relatively free to move between adjacent hydrogen-bonding sites, and a stabilization energy of approximately 8 kcal/mole per water molecule. Within the rigid dimer approximation, successive hydration of uracil is limited to the addition of one, two, or three water molecules.