Antibacterial activities of polystyrene-block-poly(4-vinyl pyridine) and poly(styrene-random-4-vinyl pyridine)

Styrene was polymerized in the presence of benzoyl peroxide (BPO) and 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) to yield polystyrene-TEMPO (PS-TEMPO) macroinitiator. The PS-TEMPO macroinitiator with different molecular weight was reacted with 4-vinyl pyridine (4-VP) to synthesize polystyrene-block-poly(4-vinyl pyridine) (PS-b-PVP), which was then quaternized with n-octyl iodide. Antibacterial activity of the quaternized copolymers was assessed against a gram negative bacterium (Pseudomonas aeruginosa) and a gram positive one (Staphylococcus aureus) by using the shake flask test method, and the results were compared with those of poly(styrene-random-4-vinyl pyridine) (P(ST-r--VP)). The quaternized copolymers inhibited greatly the growth of the bacteria, and PS-b-PVP was more active than P(ST-r-VP), which was ascribed to the fact that the content of quaternized 4-VP units on the surface of the particles of the former copolymer was higher than that corresponding to the latter one.     

Surface-enhanced raman scattering from poly(4-vinyl pyridine)

Surface-enhanced Raman scattering (SERS) has been observed for poly(4-vinyl pyridine) absorbed onto silver island films. Bands near 1219 and 1613 cm^?1, which are weak in normal Raman spectra of PVP, are strong in SERS spectra, and the band near 1020 cm^?1, which is the strongest band in the normal spectra, is relatively weak in SERS. The strongest bands in the SERS spectra all belong to the same symmetry species as α_ZZ, implying that the pyridine moieties are adsorbed through the nitrogen atoms with a vertical conformation. The ring breathing mode of the pyridine rings is observed near 1020 cm^?1, a frequency characteristic of pyridinium ions or coordinated pyridine, providing further evidence for adsorption through the nitrogen atoms. Silver catalyzed photooxidation, which can lead to the appearance of artifacts in SERS spectra, particularly of polymers, can be reduced by overcoating SERS samples with thin films of polymers such as poly(methyl methacrylate) that have low Raman scattering cross sections.     

Photoactive proton conductor: poly(4-vinyl pyridine) gel

We describe a hydrogen-bonded poly(4-vinyl pyridine)-based dielectric material, in which conductivity can be induced due to the presence of side-chain protonated species that form spontaneously when the polymer is dissolved in pyridine. The conductivity of the proton conductive gel can be controlled by direct irradiation at the proton-transfer center: a reversible change of conductivity was observed in response to the on/off switching of 385 nm wavelength radiation. Over most of the range of intensities used, the proton conductivity exhibited a bimolecular character. We present a model of the protonated pyridine side-chain unit in the ground and excited states (DFT level). In the ground state, the protonated pyridine moiety has a cyclic, conjugated structure.     

Synthesis and reactions of 4-vinyl pyridine derivatives of ruthenium(II)

4-Vinyl pyridine (4-Vp) reacts with RuHClCO(PPh₃)₃ (I) in THF to give RuHClCO(PPh₃)₂(4-Vp) (II, which reacts with sodium derivatives of bidentate chelating ligands to afford substitution products, [RuH(CO)(PPh₃)₂(L)]. The bindentate ligands used are 2-hydroxybenzaldehyde, 2-hydroxy-3-methoxybenzaldehyde, trifluorothenoylacetone and 8-hydroxyquinoline. Insertion reactions of the Ru---H bond of II with activated olefins such as acrylonitrile [giving RuCl(CO)(CH₃CHCN)(PPh₃)₂(4-Vp)], 2-vinyl pyridine, dimethyl fumarate and monobromodiethyl fumarate have been carried out to obtain chelated Ru---C bonded complexes. RuCl₂(PPh₃)₃ reacts with an excess of 4-Vp to give an octahedral ruthenium addition complex containing two vinyl pyridine ligands. The dimer [RuClCO(CH₃CHCN)(PPh₃)(4-Vp)]₂ is obtained by the reaction of [RuClCO(CH₃CHCN)(PPh₃)₂]₂ with an excess of 4-Vp. Stereochemical assignments have been made for these new complexes on the basis of IR and ¹H NMR data.     

Hybridization of poly(4-vinyl pyridine)-b-polystyrene-b-poly(4-vinyl pyridine) aggregates in dioxane/water solution

Self-assembly of binary blends of two triblock copolymers of poly(4-vinyl pyridine)-b-polystyrene-b-poly(4-vinyl pyridine), i.e., P4VP₄₃-b-PS₂₆₀-b-P4VP₄₃ (P1) and P4VP₄₃-b-PS₃₆₆-b-P4VP₄₃ (P2), in dioxane/water solution was studied. These two triblock copolymers individually tend to form vesicles (P2) and cylindrical micelles (P1) in dilute solution. It was found that copolymer components in the blend, sample preparation method, and annealing time had significant effect on hybridization aggregate morphology. By increasing P1 content in the copolymer blends, fraction of looped and stretched cylinders increased, while fraction of bilayers decreased. Nearly no bilayer was observed when P1 content was above 85 wt%. On the other hand, fraction of cylinders decreased while fraction of bilayers increased with the increase of P2 content in copolymer blends. Lamellar structures were obtained, when P2 content was 60 wt% in the copolymer blends, whereas cylinders were seldom found when P2 content was above 80 wt%. These results indicate that P1 and P2 copolymer molecules cooperatively participate in the formation of cylinders and vesicles. Some exotic structures, such as lamellae with protruding cylinders (LPC), incomplete vesicles with protruding cylinders (VPC), and cylindrical bilayers, have been kinetically trapped. These structures may result from intramicellar fusion processes in cylindrical micelles. The striking structures represent a compromise between bilayer and cylindrical geometries.     

The effects of some transition-metal compounds on the flame retardance of poly(styrene-co-4-vinyl pyridine) and poly(methyl methacrylate-co-4-vinyl pyridine)

Several copolymers of both styrene and methyl methacrylate with 4-vinyl pyridine have been prepared and modified by coordination with the transition-metal compounds vanadium acetylacetonate (VO[acac]₂), vanadyl dichloride (VOCl₂) and ferric chloride. The flame-retardant effects of these modifications have been assessed by measurements of limiting oxygen indices, by thermogravimetric analysis, and by examination of chars by scanning electron microscopy. Effects on mechanical properties have been assessed by dynamic mechanical thermal analysis. The limiting oxygen indices of the modified polymers are significantly higher than those of the parent polymers, and the production of considerable amounts of rigid, intumescent chars suggests predominantly condensed-phase mechanisms of flame retardance.     

Ion-specific swelling behaviors of partially quaternized poly(4-vinyl pyridine) gel

Swelling degrees of partially quaternized poly(4-vinyl pyridine) (p.q.P4VP) were measured as functions of the degree of quaternization (D.Q.: 5, 10, 15, 30, and 50 mol%), salt concentration (0–4 M), and salt species (KF, LiCl, NaCl, KCl, CsCl, MgCl₂, KBr, LiSCN, KSCN, Na₂SO₄, and MgSO₄) to study ion effects on the three kinds of interactions involved with p.q.P4VP in aqueous systems, i.e., electrostatic interaction, hydrogen bonding to the nitrogen of the pyridine ring, and hydrophobic interaction, as well as to estimate the relative contributions of the respective ion effects to gel swelling. Upon addition of salts at the lowest salt concentration studied (0.01 M), p.q.P4VP gels, except for one with D.Q.=10%, significantly deswelled depending on the counterion species; the lowest swelling degree was observed for the thiocyanates and the highest one for KF. In the higher salt concentration region (≧1 M) where electrostatic interactions might well be screened, however, some salt systems (e.g., LiCl, KSCN) showed swelling with increased salt concentration, contrary to the common behavior of usual ionic gels. These ion-specific swelling behaviors were interpreted as being caused by additive ionic effects on the three kinds of interactions.     

Miscibility of poly(vinyl chloride) with ethyl acrylate 4-vinyl pyridine copolymers

Blends (50:50, w:w) of poly(vinyl chloride) (PVC) and poly(ethyl acrylate-co-4-vinyl pyridine) (PEA–4-VP) of different 4-VP contents (2–14 mol %) were prepared. These were found to be partially miscible as evidenced by the presence of a single, through broad, tangent δ peak obtained from torsion pendulum experiments. Several possible types of interactions which might exist between PVC and PEA-4-VP, such as ion-dipole, crosslinking, charge transfer, hydrogen bonding, and dipole–dipole interactions, were explored. From ultraviolet, conductance, infrared, and solubility studies, it was shown that hydrogen bonding or dipole–dipole (or possibly a combination of the two) interactions were the most likely in this system. These interactions have been suggested previously for other systems by various investigators.     

Antibacterial behaviour of quaternized poly(vinyl chloride)-g-poly(4-vinyl pyridine) graft copolymers

Amphiphilic graft copolymers consisting of poly(vinyl chloride)(PVC) main chains and poly(4-vinyl pyridine)(P4VP) side chains were synthesized via atom transfer radical polymerization(ATRP) using direct initiation of chlorine atoms. The successful synthesis of PVC-g-P4 VP graft copolymers was confirmed by Fourier transform infrared spectroscopy(FTIR) and proton nuclear magnetic resonance(1H-NMR). Transmission electron microscope(TEM) and small angle X-ray scattering(SAXS) analysis showed that PVC-g-P4 VP exhibited microphase-separated, ordered structure with 37.6 nm of domain spacing, which was not observed in neat PVC. For antibacterial applications, the tertiary nitrogen atoms of PVC-gP4 VP was quaternized using 1-bromohexane, as confirmed by FTIR measurements. Bacteria including Escherichia coli(E. coli), Staphylococcus aureus(S. aureus), Bacillus cereus(B. cereus), and Pseudomonas aeruginosa(P. aeruginosa) were completely killed in 24 h on the quaternized PVC-g-P4VP(46% grafting) surface, indicating its excellent antibacterial behavior while it showed to be cytotoxic to mammalian cell.     

Grafting of 4-vinyl pyridine onto poly(vinyl alcohol) initiated by potassium diperiodatocuprate(III)

In this article, the graft copolymerization of 4-vinyl pyridine onto poly(vinyl alcohol) via the potassium diperiodatocuprate(III)-poly(vinyl alcohol) redox system as an initiator was investigated in an alkaline medium. The graft copolymer was characterized with Fourier-transform infrared spectra analysis. A mechanism is proposed to explain the generation of radicals and the initiation. The effects of reaction variables, such as the initiator concentration, the ratio of monomer to poly(vinyl alcohol), pH, and reaction temperature and time, are investigated, and the grafting conditions are optimized. Graft copolymers with high grafting efficiency are obtained, thus indicating that potassium diperiodatocuprate(III)-PVA redox system is an efficient initiator for this graft copolymerization. Published in Russian in Vysokomolekulyarnye Soedineniya, Ser. B, 2006, Vol. 48, No. 7, pp. 1190–1194. This text was submitted by the authors in English.     

The synthesis and properties of adducts between poly(4-vinyl pyridine) and metal alkyls

Poly(4-vinyl pyridine) is used as a polymeric ligand to react with metal alkyls, Me_nM (n = 3, M = Al, Ga or In; n = 2, M = Cd or Zn) to form adducts. The adducts are characterized by solid state ¹³C NMR, infrared spectroscopy, microanalyses and differential scanning calorimetry (DSC). All the adducts are nonpyrophoric and thermally dissociable, so they may have potential both for use in adduct purification processes or for use as safer metal alkyl sources for Metal–Organic Chemical Vapor Deposition.     

Kinetics and mechanism of the quaternization of poly(4-vinyl pyridine) with 1-bromopropane

The kinetics of the quaternization of poly(4-vinyl pyridine) with 1-bromopropane in sulfolane has been studied in the temperature range 308–348°K with data points covering the whole conversion range. The results have been analyzed according to the neighbouring-group model with rate constants k₀, k₁, and k₂ for reaction of pyridyl groups with zero, one, and two already reacted neighbors. Allowing for limiting reaction at about 95%, the experimental results substantiate the model with K = k₁/k₀ = 0.80 ± 0.03, and L = k₂/k₀ = 0.37 ± 0.03, which are independent of temperature. The temperature dependence of k₀ values gives an activation energy of 66.22 ± 4.20 kJ mol^?1. It is still not possible to decide whether steric or electrostatic factors are responsible for K and L values less than unity. Other systems are mentioned where side reactions occur.     

Preparation and pH triggered inversion of vesicles from poly(acrylic acid)-block-polystyrene-block-poly(4-vinyl pyridine)

The aggregate morphologies of the biamphiphilic triblock PAA(26)-b-PS(890)-b-P4VP(40) have been studied by TEM as a function of pH in DMF/THF/H(2)O mixtures. The outside surfaces of the aggregates were characterized by zeta potential measurements. Starting at the apparent pH (pH) of 1, and increasing gradually to pH14, the aggregate morphologies of this triblock change progressively from vesicles (pH1), to solid spherical or ellipsoidal aggregates (pH3 approximately 11), and finally back to vesicles (pH14). Vesicles prepared at pH1 contain P4VP chains on the outside and PAA chains on the inside, while those prepared from the same triblock at pH14 contain PAA outside and P4VP inside. The segregation is based on the difference in repulsive interactions within the PAA or P4VP corona under different pH conditions. At low pH, the curvature is stabilized through increased repulsive interactions between the P4VP chains on the outside relative to the less repulsive interactions between the PAA chains on the inside. At pH14, by contrast, the PAA is preferentially segregated to the outside and the P4VP to the inside because of the increased repulsive interaction between PAA chains and the decreased repulsive interaction between P4VP chains at high pH. Most importantly, vesicles with PAA on the outside can be inverted to P4VP on the outside by changing the pH while the vesicles have swollen cores and are under dynamic conditions. The conversion mechanism is suggested to involve a whole vesicle process because the CMC is far too low for single chain reassembly to be involved.     

Surface-enhanced Raman scattering from bilayers of polystyrene,diglycidyl ether of bisphenol-A,poly(4-vinyl pyridine), and poly(4-styrene sulfonate)

Surface-enhanced Raman scattering (SERS) has been observed from thin films of polystyrene (PS), diglycidyl ether of bisphenol-A (DGEBA), and poly(4-vinyl pyridine) (PVP) deposited on silver island films Degradation of the polymers occurred rapidly during laser irradiation and was accompanied by the appearance of strong bands near 1375 and 1575 cm-1. These bands were attributed to the formation of graphite-like species by the silver-catalyzed thermal oxidation of the polymers induced by localized laser heating of the substrate. When the thin films of PS, DGEBA, or PVP were overcoated with much thicker films of a second polymer such as polystyrene sulfonate (PSS), the degradation was greatly reduced, and excellent SERS spectra of the PS, DGEBA, and PVP films were obtained. Overlayers reduced degradation within the first films deposited on silver island films by restricting the availability of oxygen at the interface to its solubility in the overlayer polymer or by altering the adsorption of oxygen onto the substrate. SERS was observed for the PS, DGEBA, and PVP films and the PSS overlayers when the films were deposited from relatively dilute solutions. When the PS, DGEBA, and PVP films were deposited from more concentrated solutions, SERS was not observed from the PSS overlayers. It was suggested that most of the SERS was due to a short-range, charge-transfer mechanism associated with sites of atomic scale roughness and that SERS was observed from the overlayer when the first film failed to occupy all of the sites.     

聚苯乙烯-聚(4-乙烯基吡啶)嵌段共聚物LB膜结构形态的研究

采用氯仿作为铺展溶剂,将嵌段共聚物聚苯乙烯-聚(4-乙烯基吡啶)(PS-b-P4VP)稀溶液铺展于空气与水界面上,利用Langmuir-Blodgett(LB)膜技术转移至固体基底.研究了不同的嵌段比、表面压和小分子1-芘丁酸(PBA)的加入对嵌段共聚物气液界面聚集组装的影响.研究发现随着亲水段(P4VP)的增加,聚集组装结构由纳米片状、带状转变成纳米条状、纳米点状结构.表面压对纯PS-b-P4VP聚集组装产生影响,表面压增大,组装体排列紧密;随着表面压的继续增大,单层聚集结构遭到破坏,发生堆叠.加入PBA小分子后,PBA与PS-b-P4VP形成氢键,形态发生明显变化,原来的片状结构转变为条状或点状结构.     

Ionic miscibility enhancement via microion elimination in sulfonated polystyrene/poly(ethyl-acrylate-co-4-vinyl pyridine) ionomer blends

Miscibility enhancement of ionomer/ionomer and ionomer/polymeric acid systems is studied on the polymer pairs of poly(styrene-co-tetramethyl ammonium styrenesulfonate)/poly(ethyl acrylate-co-N-methyl-4-vinylpyridinium iodide) and poly(styrene-co-styrenesulfonic acid)/poly(ethyl acrylate-co-N-methyl-4-vinylpyridinium iodide). NMR and dynamic mechanical results show that in these blends direct macroion–macroion interaction can be achieved with the elimination of microcounterions from the polymer chains. Ion-ion attraction leads to a miscibility enhancement comparable to that of the previously reported proton transfer blends; a miscible blend is obtained with ca. 5 mol% of ions in the polymers.     

Glass transition of thin films of poly(2-vinyl pyridine) and poly(methyl methacrylate): nanocalorimetry measurements

Glass transitions were observed in thin films of poly(2-vinyl pyridine) (P2VP) and poly(methyl methacrylate) (PMMA) using a scanning nanocalorimetry technique which has both high sensitivity (10⁻⁹ J/K) and high scan rates (10⁴-10⁵ K/s). Samples were deposited by the spin-cast method. The thickness of samples was 100-400 nm. Glass transition temperature, obtained by nanocalorimetry, is shifted toward higher temperatures by 10-20 K and activation enthalpy of glass transition is shifted to lower values by factor of 2-4. The glass transition characteristics of both polymers are discussed in terms of the standard Tool-Narayanaswamy-Moynihan (TNM) multi-parameter model.     

Influence of chain conformation on translational diffusion of poly(2-vinyl pyridine) in dilute solution

A comparative photon correlation spectroscopy study is reported of the concentration-dependent translational diffusion coefficient D_t of atactic poly(2-vinyl pyridine) in tetrahydrofuran and in aqueous solution, in the form of the poly(2-vinyl pyridinium)chloride salt (α = 0.4). The limiting Stokes radius of the polymer is observed to be identical within experimental error in tetrahydrofuran (THF) at temperatures below 30°C and in aqueous solutions at high ionic strength. This numerical value is comparable to expectation for an unperturbed atactic vinyl polymer chain and indicates a compact, possibly micellar, conformation. Raising the temperature in THF above 30°C and decreasing the ionic strength or increasing the ionization above α = 0.4 in aqueous solvents causes a discontinuous cooperative transition to a more expanded structure. The effect of the conformational change is also manifest in the concentration dependence of D_t. Using experimental estimates of the second osmotic virial coefficients obtained by total scattered intensity measurements, the experimental data for dD_t/dc are compared with prediction based on hydrodynamic theory. Substantial disagreement is found between theory and experiment, especially in the aqueous system. In 0.01M NaCl, decrease in polyion concentration induces the transition from the compact form to a highly extended structure. Angle-dependent quasielastic light scattering data from the expanded state provides information about the intramolecular chain dynamics.     

Synthesis,characterization and thermal behaviour of some poly(2-vinyl pyridine) complexes

Poly(2-vinyl pyridine) complexes were prepared via quaternization of the ring nitrogen with different reagents (I₂, Br₂, Cl₂, CrO₃, picric acid and HgCl₂). The thermal behaviour of these polymer complexes, such as E and the order of decomposition, were studied by using the modified Freeman and Carroll procedure. Generally, it was found that the presence of a substituent on the nitrogen in the polymer lowers the activation energy and the thermal stability.

---

Zusammenfassung Durch Quaternierung von Ring-Stickstoffatomen mit verschiedenen Reagenzien (I₂, Br₂, Cl₂, CrO₃, Pikrinsäure, HgCl₂). wurden Poly(2-vinylpyridin)komplexe hergestellt. Unter Anwendung der modifizierten Freeman and Carroll Methode wurde das thermische Verhalten dieser Polymerkomplexe untersucht, wie z.B. E und Reaktionsordnung der Zersetzungsreaktion. Allgemein wurde festgestellt, daß die Anwesenheit einer Gruppe am Stickstoff im Polymer die Aktivierungsenergie senkt und seine thermische Stabilität verringert.