ANTIBACTERIAL ACTIVITY OF SINGLE AND MIXED AMMONIUM AND PHOSPHONIUM SALTS GRAFTED ON "GEL-TYPE" STYRENE-DIVINYLBENZENE COPOLYMERS*

1.INTRODUCTIONThesynthesisofpolymer-supported"onium"salts(ammoniumandphosphonium)(1~5(wasdiscussedindetailduetothewidefieldofutilizationas:polarstationaryphasesforanionchromatography(6(,polymericreagentsfortrans-quaternizationreactions(7,8(,phase-transfercatalysts(9~13(andpolycationicbiocides(14~17(.Manychemicalmaterialssuchasozone,liquidchlorine,sodiumhydrochloride,s.a.,havebeenlargelyusedtosterilizeairandwater.Suchmaterialsrequirespecialequipmentandcarelessusemaycauseenvironmentalpolluti…     

Preparation, characterization and application of ZnO sol containing quaternary ammonium salts

The zinc oxide sol containing quaternary ammonium salts (DMDAAC-ZnO) was synthesized by zinc acetate and dimethyldiallyl ammonium chloride via the sol–gel process. Effects of zinc acetate concentration, diethanolamine dosage and dimethyldiallyl ammonium chloride dosage on the absorbance-ratio and viscosity of the sol were investigated. Zinc oxide sols were characterized by XRD, TEM and FT-IR. DMDAAC-ZnO was applied to cotton samples and cotton samples treated were tested by antibacterial activity, UV resistance and breaking strength. The antibacterial activity and UV resistance of samples treated by zinc oxide sol containing quaternary ammonium salt were both better than sample treated by zinc oxide sol.     

Biotreatment on Cellulose Fluff Pulp: Quaternary Ammonium Salts Finish and Grafting with β-cyclodextrin

For its potential performances to be expanded, cellulose needs to be processed in different ways. Therefore, an object of the present work was to provide a chemical modification of cellulose through: a specific finish with two quaternary ammonium salts (namely Aliquat 336 and Aliquat 1529, respectively). Chemical grafting of β-cyclodextrin derivative (β-CD) onto fibers followed by the inclusion of benzoic acid in the grafted CD cavities as a probe chemical. Physicochemical properties and performances of the untreated and treated fibers have been determined with infrared spectra, microscopy, swelling measurements, antimicrobial finishing tests, and dye adsorption. Our results show that cellulose fibers can be efficiently modified with no significant changes in its structural and surface properties; the treated fibers show an attractive behavior in swelling, dye adsorption and antibacterial activity.     

Modified gelatin with quaternary ammonium salts containing epoxide groups

An EPDDMAC-GE polymer （hydrophilic molecule） has been synthesized based on epoxypropyl dodecyl dimethyl ammonium chloride （EPDDMAC） and gelatin. A DEEPSAC-GE polymer （hydrophobic molecule） has been synthesized based on diethyl-2,3-epoxypropyl-[3-methyldimethoxyl] silpropyl ammonium chloride （DEEPSAC） and gelatin. Compared with initial gelatin, the gelatin modified with quaternary ammonium salts containing epoxide groups exhibits stronger antibacterial activity.     

Reversible pH-controlled switching of poly(methacrylic acid) grafts for functional biointerfaces

Responsive polymeric brushes of poly(methacrylic acid) (PMAA) were grafted from silicon surfaces using controlled surface-initiated atom-transfer radical polymerization (SI-ATRP). The growth kinetics of PMAA was investigated with respect to the composition of the ATRP medium by grafting the polymer in mixtures of water and methanol with different ratios. The dissociation behavior of the polymer layers was characterized by FTIR titration after incubating the polymer-grafted substrates in PBS buffer solutions with different pH values. PMAA layers show a strong pH-dependent behavior with an effective pK(a) of the bulk polymer brush of 6.5 ± 0.2, which is independent of the polymer brush thickness and methanol content of the ATRP grafting medium. The pH-induced swelling and collapse of the grafted polymer layers were quantified in real time by in situ ellipsometry in liquid environment. Switching between polymer conformations at pH values of 4 and 8 is rapid and reversible, and it is characterized by swelling factors (maximum thickness/minimum thickness) that increase with decreasing the methanol content of the SI-ATRP medium.     

Controlled nitroxide-mediated styrene surface graft polymerization with atmospheric plasma surface activation

Polymer layer growth by free radical graft polymerization (FRGP) and controlled nitroxide-mediated graft polymerization (NMGP) of polystyrene was achieved by atmospheric pressure hydrogen plasma surface activation of silicon. Kinetic polystyrene layer growth by atmospheric pressure plasma-induced FRGP (APPI-FRGP) exhibited a maximum surface-grafted layer thickness (125 A after 20 h) at an initial monomer concentration of [M] 0 = 2.62 M at 85 degrees C. Increasing both the reaction temperature ( T = 100 degrees C) and initial monomer concentration ([M] 0 = 4.36 M) led to an increased initial film growth rate but a reduced polymer layer thickness, due to uncontrolled thermal initiation and polymer grafting from solution. Controlled atmospheric pressure plasma-induced NMGP (APPI-NMGP), using 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO), exhibited a linear increase in grafted polystyrene layer growth with time due to controlled surface graft polymerization as well as reduced uncontrolled solution polymerization and polymer grafting, resulting in a polymer layer thickness of 285 A after 60 h at [TEMPO] = 10 mM, [M] 0 = 4.36 M, and T = 120 degrees C. Atomic force microscopy (AFM) surface analysis demonstrated that polystyrene-grafted surfaces created by APPI-NMGP exhibited a high surface density of spatially homogeneous polymer features with a low root-mean-square (RMS) surface roughness ( R rms = 0.36 nm), similar to that of the native silicon surface ( R rms = 0.21 nm). In contrast, polymer films created by APPI-FRGP at [M] 0 = 2.62 M demonstrated an increase in polymer film surface roughness observed at reaction temperatures of 85 degrees C ( R rms = 0.55 nm) and 100 degrees C ( R rms = 1.70 nm). The present study concluded that the current approach to APPI controlled radical polymerization may be used to achieve a grafted polymer layer with a lower surface roughness and a higher fractional coverage of surface-grafted polymers compared to both conventional FRGP and APPI-FRGP.     

POLYMER—SUPPORTED SINGLE AND MIXED AMMONIUM AND PHOSPHONIUM SALTS AS CATALYSTS FOR PHASE—TRANSFER REACTIONS

In this study was to investigate,by phase-transfer catalysis,the activity of single and mixed ammonium and phosphonium salts grafted on a “gel-type“ stryene-7% divinylbenzene copolymer in the oxidation of benzyl alcohol with hydrogen peroxide.A wide variety of catalysts with different quaternary groups and different quaternary chain length substitutents were examined.The activity of single“onium“salts increases as a consequence of the association of ammonium and phosphonium salts grafted onn the same polymeric support.The activity of polymer-supported ammonium and phosphonium salts increases with the number of carbon atoms contained in the alkyl radicals of the -onium and of the functionalization degree with phosphonium groups.     

Inorganic surface nanostructuring by atmospheric pressure plasma-induced graft polymerization

Surface graft polymerization of 1-vinyl-2-pyrrolidone onto a silicon surface was accomplished by atmospheric pressure (AP) hydrogen plasma surface activation followed by graft polymerization in both N-methyl-2-pyrrolidone (NMP) and in an NMP/water solvent mixture. The formation of initiation sites was controlled by the plasma exposure period, radio frequency (rf) power, and adsorbed surface water. The surface number density of active sites was critically dependent on the presence of adsorbed surface water with a maximum observed at approximately a monolayer surface water coverage. The surface topology and morphology of the grafted polymer layer depended on the solvent mixture composition, initial monomer concentration, reaction temperature, and reaction time. Grafted polymer surfaces prepared in pure NMP resulted in a polymer feature spacing of as low as 5-10 nm (average feature diameter of about 17 nm), an rms surface roughness range of 0.18-0.72 nm, and a maximum grafted polymer layer thickness of 5.5 nm. Graft polymerization in an NMP/water solvent mixture, however, resulted in polymer feature sizes that increased up to a maximum average feature diameter of about 90 nm at [NMP] = 60% (v/v) with polymer feature spacing in the range of 10-50 nm. The surface topology of the polymer-modified silicon surfaces grafted in an NMP/water solvent mixture exhibited a bimodal feature height distribution. In constrast, graft polymerization in pure NMP resulted in a narrow feature height distribution of smaller-diameter surface features with smaller surface spacing. The results demonstrated that, with the present approach, the topology of the grafted polymer surface was tunable by adjusting the NMP/water ratio. The present surface graft polymerization method, which is carried out under AP conditions, is particularly advantageous for polymer surface structuring via radical polymerization and can, in principle, be scaled to large surfaces.     

PMMA/MMT nanocomposites prepared by one-step in situ intercalative solution polymerization

Poly(methylmetacrylate)/montmorillonite (PMMA)/(MMT) nanocomposites were prepared by one-step in situ intercalative solution polymerization involving simultaneous modification of MMT with quaternary ammonium salts (QAS), polymerization and polymer intercalation. Polymerization proceeded at 70 °C in a mixture of ethanol and water, whereas the nanocomposite was precipitated with only water. Four QAS’s with different alkyl chain lengths, as well as a QAS with an additional acrylic group, were used to study the influence of the type of quaternary ammonium salt on intercalation. The largest extent of intercalation was achieved in nanocomposites with the QAS having one long alkyl (C16) chain. The obtained PMMA/MMT intercalated nanocomposites exhibited a higher glass transition temperature, better thermal stability, and improved solvent resistance than the pure PMMA.     

A general method to determine ionization constants of responsive polymer thin films

A general method has been developed to determine the ionization constants of polymer thin films based on the stimuli-responsiveness of the polymer. Robust polymer films were fabricated on silicon wafers and gold slides using perfluorophenyl azide (PFPA) as the coupling agent. The ionization constants were measured by a number of techniques including ellipsometry, dynamic contact angle goniometry, and surface plasmon resonance imaging (SPRi). Using poly(4-vinylpyridine) (P4VP) as the model system, P4VP thin films were fabricated and the ionization constants of the films were measured taking advantage of the pH responsive property of the polymer. The pK(a) determined by ellipsometry, ~4.0, reflects the swelling of the polymer film in response to pH. The pK(a) value calculated from the dynamic contact angle measurements, ~5.0, relies on the change in hydrophilicity/hydrophobicity of the films as the polymer undergoes protonation/deprotonation. The pK(a) value measured by SPRi, ~4.9, monitors in situ the change of refractive index of the polymer thin film as it swells upon protonation. This was the first example where SPRi was used to measure the ionization constants of polymers.     

Swelling of a polymer brush by a poor solvent

The addition of a small amount of a poor solvent impurity (methanol) to a theta solvent (cyclohexane) is found to cause appreciable swelling (≈30% increase of the average brush height) in a model end‐grafted polystyrene (PS) brush layer. This unusual type of swelling is not observed if octadecyltrichlorosilane (OTS) is first grafted to the portion of the silicon substrate uncovered by the grafting end‐groups of the PS chains. Brush swelling in the absence of OTS surface protection is interpreted as arising from a segregation of methanol to the solid substrate and the resulting modification of the polymer–surface interaction. We also observe that the addition of a small amount of methanol to an adsorbed PS layer exposed to cyclohexane causes rapid film delamination from the silicon substrate. Together these observations imply a strong influence of surface active impurities on the structure and adhesive stability of polymer layers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4126–4131, 2004     

The antibacterial finish of cotton via sols containing quaternary ammonium salts

The sols containing quaternary ammonium salts were prepared via sol-gel process. The effects of the molar rate of HCl, H₂O and EtOH to TEOS on the sol viscosity were investigated in detail. Cetyltrimethylammonium bromide (CTAB), Octadecyl dimethyl benzyl ammonium chloride (DC) and Ethylene-Bis (Octadecyl trimethyl ammonium chloride) [E-Bis(OTAC)]were added in the sols and applied to cotton samples by treated. The antibacterial activities of the samples were assessed against both Escherichia coli and Staphylococcus aureus bacteria. The samples treated by E-Bis(OTAC) sol exhibited the satisfactory antibacterial activity that resulted from the more microorganism adsorption and hydrophobicity. The antibacterial activities were still excellent after 10 times washings comparison with the control samples.     

Controlled pore functionalization of poly(ethylene terephthalate) track-etched membranes via surface-initiated atom transfer radical polymerization

A new method for surface-initiated atom transfer radical polymerization (ATRP) on the technical polymer poly(ethylene terephthalate) (PET) has been developed which allows controlling and estimating the layer thickness of the grafted polymer in the isocylindrical pores of track-etched membranes. After PET surface treatment by oxidative hydrolysis, the bromoalkyl initiator was immobilized on the PET surface in a two-step solid-phase reaction; the isoporous membrane structure was preserved, and the pore diameter was increased from 760 to 790 nm. Poly(N-isopropylacrylamide) (PNIPAAm) was grafted under ATRP conditions from a methanol/water mixture at room temperature. Both monomer concentration and reaction time could be used as parameters to adjust the degree of grafting. Effective grafted layer thickness and its response to temperature were estimated from pure water permeability. All data, especially the high polymer densities (0.37 g/cm3) in the swollen layers at 25 degrees C, indicate that grafted PNIPAAm with a "brush" structure has been achieved. For dry PNIPAAm layer thicknesses on the PET pore walls of up to 80 nm, a temperature-induced swelling/deswelling ratio of approximately 3 had been observed. Reduction of the brush grafting density, via composition of the reaction mixture used in solid-phase synthesis for initiator immobilization, led to an increase of that swelling/deswelling ratio. Further, density and temperature response of the grafted PNIPAAm layers synthesized via ATRP were compared with those obtained in the same membranes by less controlled photografting, leading to lower grafting density and larger gradients in grafted layer density and, consequently, much higher swelling/deswelling ratios (>15).     

Effect of chain length on the interaction between modified organic salts containing hydrocarbon chains and poly(N-isopropylacrylamide-co-acrylic acid) microgel particles

A series of four hydrophobically modified, diphenylazo-based organic salts have been prepared and characterized. To achieve this a C(x) (x = 4, 6, 8, or 10) hydrocarbon chain was inserted between the diphenylazo moiety and the quaternary ammonium headgroup of the salt. The absorption of each of the four modified organic salts into anionic microgel particles of poly(N-isopropylacrylamide-co-acrylic acid) has been studied at pH 8. In addition, the hydrodynamic diameters and electrophoretic mobilities of the microgel particles have been studied as a function of the organic salt concentration, also at pH 8. In addition to the electrostatic attraction between the quaternary ammonium head groups of the organic salts and the anionic groups within the microgel particles, hydrophobic association between the chains of the organic salts within the microgel particles plays a role, with this effect increasing strongly from x=4 to 10. Desorption of the x=4 and 6 organic salts occurs readily on changing, in situ, the pH from 8 to 2.5 (and thereby eliminating the electrostatic interaction) but is only partially achieved for the x=8 and 10 organic salts. Indeed, for the x=10 organic salt, only about 80% of the organic salt is desorbed upon dilution of the microgel particles into a large excess of water.     

Abtrennung quartärer Ammoniumverbindungen über zerlegbare Ionenpaarextrakte mit nachfolgender Identifizierung

Ion-pairs of quaternary ammonium salts with lipophilic anions may be extracted into an organic layer. By using such anions capable to loose their negative charge by protonization (pH shiftment), the ion-pair separated with the organic solvent will be split by treatment with aqueous acids. Of the substances investigated, 6-phenyl-2,4-dinitrophenol seems the most promising. Surplus volatile acid may be removed in vacuo, leaving the quaternary salt as residue. Identification is accomplished by UV spectra of the aqueos solutions and TLC. Interesting observations in the search for spray reagents were: the probable ion-pair nature of the “Dragendorff” complexes, colour reactions of quaternary pyridinium derivatives with potassium hexacyanoferrat(II), and dark spots given by quaternary salts with mercury(I) nitrate on alumina layers.     

Preparation and Antibacterial Function of Quaternary Ammonium Salts Grafted Cellulose Fiber Initiated by Fe2 +-H2O2 Redox

The surface contact disinfecting technique is a newly developed method for water sterilization. In this paper, the grafted quaternary ammonium salts (QAS) antibacterial fibers were prepared and designed to apply for the surface contact disinfecting process in water treatment. The antibacterial fibers were directly prepared by grafting methacryloxylethyl benzyl dimethyl ammonium chloride (DMAE-BC) onto cellulose fiber using thiocarbonate-H₂O₂ redox system. All kinds of factors in the grafting reactions, such as reaction time, reaction temperature, monomer concentration, initiator concentration, which influence the percentage of grafting, were studied and optimized. The modified cellulose fibers were characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscope(SEM). The effects of the percentage of grafting of the grafted cellulose fibers on bactericidal activity were also studied. The spread plate method was used to characterize the bactericidal activity. The disinfection process was further investigated by directly observing the morphology of the bacterial cells adsorbed on the antibacterial fibers with SEM and measuring extracelluar total protein concentration in suspension. The poly(DMAE-BC)-grafted cellulose ?ber was found to exhibit particularly high activity against E.coli.     

A novel UV-sensitive photopolymerization system with microgel matrix

A series of crosslinked microgels with quaternary ammonium ions on the surface was prepared by quaternization with N,N-dimethylbenzylamine in the presence of microgel particles prepared by emulsion copolymerization of styrene (St), chloromethylstyrene (CMS) and divinylbenzene (DVB). Microgels with diameters in the range of 15–100 nm were successfully dispersed in organic solvents such as 2-methoxyethanol and 2-ethoxyethanol without an emulsifier. A photosensitive layer was formed by coating a photosensitive solution on a grained aluminum plate. The solution was comprised of the microgels, the multifunctional monomer and standard ultraviolet (UV) photoinitiators, such as 2,4-diethyl thioxanthone (DETX)/ethyl p-di-ethylaminobenzoate (EPA). This gave a heterogeneous photosensitive layer which produced good polymer patterns after exposure to UV light followed by development in tap water. A typical polymer layer, consisting of the microgels (poly(styrene-co-N,N-dimethylbenzylvinyl-benzylammonium chloride-co-divinylbenzene)), DETX/EPA, and the multifunctional acrylate monomers, exhibited photosensitivity of 0.06 mJ/cm² for UV light. This sensitivity is much higher than the homogeneous photopolymerization system with an analogous composition.     

Inhibitory activity of fluorine-containing quaternary ammonium salts comprising an N-methylpiperazinyl moiety

New fluorine-containing quaternary ammonium salts comprising an N-methylpiperazinyl moiety, which exhibited a high inhibiting capacity against hydrochloric acid corrosion of low-carbon steel, were synthesized. The polarization-resistance method was applied to determine the uniform corrosion rate of steel-3 in relation to the structure and concentration of the fluorine-containing substituents in the salts. It was found that the structure of the fluorine-containing moiety of the quaternary ammonium salts does not significantly influence the corrosion processes.     

溴化苄基取代吡啶类季铵盐的制备和抗菌性能

抗菌材料和抗菌制品的研究与应用一直是世界各国研究的重要课题~([1-3]),其中有机抗菌剂占据主要地位.季铵盐是研究比较多的一类有机抗菌剂,它们表现出良好的物理性质,如胶束浓度低,黏弹性好和溶解性强~([4]),同时此类抗菌剂具有强效的抗菌作用~([5]),引起了人们的极大兴趣.季铵盐广泛应用于医药、卫生、食品、饲料工业、农业、纺织、塑料、橡胶、造纸、水处理、油田开采、涂料、日常生活等多种领域~([6-10]).     

Hyperbranched Polymer Induced Antibacterial Tree-Like Nanofibrous Membrane for High Effective Air Filtration

The air filtration materials with high efficiency, low resistance, and extra antibacterial property are crucial for personal health protection. Herein, a tree-like polyvinylidene fluoride (PVDF) nanofibrous membrane with hierarchical structure (trunk fiber of 447 nm, branched fiber of 24.7 nm) and high filtration capacity is demonstrated. Specifically, 2-hydroxypropyl trimethyl ammonium chloride terminated hyperbranched polymer (HBP-HTC) with near-spherical three-dimensional molecular structure and adjustable terminal positive groups is synthesized as an additive for PVDF electrospinning to enhance the jet splitting and promote the formation of branched ultrafine nanofibers, achieving a coverage rate of branched nanofibers over 90% that is superior than small molecular quaternary ammonium salts. The branched nanofibers network enhances mechanical properties and filtration efficiency (99.995% for 0.26 µm sodium chloride particles) of the PVDF/HBP-HTC membrane, which demonstrates reduced pressure drop (122.4 Pa) and a quality factor up to 0.083 Pa⁻¹ on a 40 µm-thick sample. More importantly, the numerous quaternary ammonium salt groups of HBP-HTC deliver excellent antibacterial properties to the PVDF membranes. Bacterial inhibitive rate of 99.9% against both S. aureus and E. coli is demonstrated in a membrane with 3.0 wt% HBP-HTC. This work provides a new strategy for development of high-efficiency and antibacterial protection products.