氟化修饰显著提高碳点的抗菌活性

本文采用支化聚乙烯亚胺和乙醇制备阳离子碳点,并在其表面接枝含氟烷基链,得到一种氟化修饰的碳点材料,其对革兰氏阳性菌金黄色葡萄球菌以及革兰氏阴性菌大肠杆菌和绿脓杆菌都表现出了优异的抗菌活性,而对哺乳动物细胞具有较低的毒性。通过构效关系研究发现,氟化修饰对于碳点的抗菌活性至关重要,将含氟烷基链替换成烷烃基链会极大削弱碳点的抗菌性能。本文的结果为阳离子抗菌材料的设计提供了新的思路。     

Structure and surface properties of polyacrylates with short fluorocarbon side chain: Role of the main chain and spacer group

The degradation of poly(fluoroalkyl acrylate)s with long perfluoroalkyl groups, especially with perfluorooctyl group, leads to the release of biopersistent perfluorooctanoic acid (PFOA) or perfluorooctanesulfonic acid (PFOS). To find the environmentally friendly substitutes, a series of nonbiopersistant fluorinated polymers containing perfluorohexyl groups in the side chains have been synthesized and characterized. This study was then focused on the role played by the main chain and spacer group located in the side chain between the backbone and the fluorinated segment and, in particular, on the properties of poly[2‐[[[[2‐(perfluorohexyl)]‐sulfonyl]methyl]amino]ethyl] acrylate (PC6SA), methacrylate (PC6SMA) and poly[(perfluorohexyl)ethyl] methacrylate (PC6MA). Surface properties and bulk organization of fluorinated side chains of those polymers were investigated by contact angles, differential scanning calorimetry, optical polaring microscopy, and wide‐angle X‐ray scattering. Results were compared with those obtained with poly[(perfluorohexyl) ethyl] acrylate (PC6A). They all had very low surface free energies. Surprisingly, with the same perfluoalkyl chain, PC6SA and PC6SMA with a N‐methylsulfonamide spacer group were found to be organized in a liquid crystalline lamellar structure, whereas PC6A and PC6MA were found to be amorphous. This was mainly attributed to the steric term and polarity of N‐methylsulfonamide group that tended to facilitate the orientation of the perfluorinated segments in smectic phases. PC6SA, PC6SMA, and PC6MA had rich dynamic water repellency because of the low surface molecular mobility. This phenomenon relates to the crystallization of side chains or high glass transition temperature. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2584–2593, 2010     

Nonaqueous Emulsions – A Versatile Tool for New Types of Functional Nanoparticles

Summary : The preparation of functional polymer latex particles is usually carried out in aqueous heterogeneous systems, i.e. for example in emulsion or mini-emulsion polymerization. Due to the presence of water, moisture sensitive reactions like step growth polymerizations or metal catalyzed reactions can not be accomplished without side reactions and / or decomposition. In order to avoid these side reactions, different nonaqueous emulsion systems have been developed. According to the desired polymerization procedure, these systems consist of a nonpolar organic phase surrounded by a perfluorinated solvent or of a polar organic phase which is dispersed in a nonpolar organic solvent. Both emulsions are stabilized by amphipolar block copolymers and result in long time stable particle dispersions. The resulting dispersions yield particles with narrow size distributions and – depending on the reaction conditions – diameters down to tens of nanometers. This technique allows the formation of particles consisting of numerous different classes of polymers, e.g. polyurethanes, polyesters, polyolefins etc. and the formation of more complex morphologies such as core shell structures.     

Novel and facile synthesis of fluorinated enamino ketones and amino alcohols

Selected imines and one bis-imine react via their enamine tautomers with terminal perfluorinated epoxides, e.g. hexafluoropropene oxide to produce fluorinated enamino ketones or imino ketones. In contrast, internal perfluorinated linear epoxides and one cyclic epoxide yield intermediate imino alcohols, which in one case added hexafluoroacetone, furnishing a new imino diol investigated by X-ray diffraction.     

New mesogen with thermotropic cubic phase: 3,4,5‐tris‐(11,11,12,12,13,13,14,14,15,15,16,16,16‐tridecafluorohexadecyloxy)benzoic acid

A new mesogen, 3,4,5‐tris(11,11,12,12,13,13,14,14,15,15,16,16,16‐tridecafluoro‐hexadecyloxy)benzoic acid, with a thermotropic cubic phase was synthesized. The phase behaviour of the fluorinated compound and its corresponding non‐fluorinated analogue was investigated by differential scanning calorimetry, polarizing optical microscopy, and synchrotron small‐angle X‐ray diffraction. The fluorinated compound, which contains three partially perfluorinated alkoxy moieties and one carboxylic acid group capable of forming hydrogen bonding, exhibits a very interesting sequence of isotropic, cubic and hexagonal columnar phases, whereas its non‐fluorinated compound does not have a liquid crystalline phase. The cubic phase exists over a wide temperature range (from ～200°C to ～30°C on cooling) and is hence amenable to various physical measurements and potential applications. The ability to self‐assemble molecules into ordered superstructure via both partially perfluorinated chains and hydrogen bonding provides new insight for the development of novel liquid crystalline materials.     

Preparation of colloidal stable fluoroalkyl end‐capped oligomer/silver nanocomposites––application to the surface modification of traditional organic polymers with these nanocomposites

A variety of fluoroalkyl end‐capped oligomers/silver nanocomposites were prepared by the reactions of silver ions with poly(methylhydrosiloxane) in the presence of fluoroalkyl end‐capped N,N‐dimethylacrylamide oligomer, N‐(1,1‐dimethyl‐3‐oxobutyl)acrylamide oligomer, N,N‐dimethylacrylamide cooligomer containing poly(dimethylsiloxane) segments in organic media such as toluene and 1,2‐ dichloroethane. These fluorinated oligomers/silver nanocomposites thus obtained were found to exhibit clear plasmon absorption bands around 420 nm related to the formation of silver nanoparticles. In particular, these composites could display narrow plasmon absorptions around 420 nm in toluene by the addition of trioctylamine (TOA). On the other hand, the corresponding non‐fluorinated N‐(1,1‐ dimethyl‐3‐oxobutyl)acrylamide oligomer was not able to afford such a plasmon absorption under similar conditions. These fluorinated oligomers/silver nanocomposites in organic media have been found to be stable for more than 10 days. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) measurements showed that silver nanoparticles could be effectively encapsulated into fluorinated oligomeric aggregate cores to afford colloidal stable fluorinated oligomers/silver nanocomposites. Fluorinated oligomers/silver nanocomposites were also applied to the surface modification of traditional organic polymers such as polystyrene (PSt) and poly(methyl methacrylate) (PMMA) to exhibit not only a good oleophobicity imparted by fluorine but also a higher surface antibacterial activity related to the silver nanoparticles on their surface. Copyright © 2007 John Wiley & Sons, Ltd.     

Preparation and Antibacterial Effect of Bamboo Charcoal/Ag on Staphylococcus Aureus and Pseudomonas Aeruginosa

Bamboo charcoal supporting silver (BC/Ag) was prepared by activation and chemical reduction. The BC/Ag composites were characterized by silver particle size and distribution, silver ion (Ag⁺) release and antibacterial properties. Scanning and transmission electron microscopy (SEM and TEM) showed that the Ag particles were distributed uniformly on the BC matrix. The Ag particle size was found to be less than 150 nm based on TEM. The Ag⁺ release increased initially which was followed by a marginal increase between the 8th and 24th hour. Composites contained higher amounts of silver exhibited a further rise in Ag⁺ release from the 24‐hours of storage in water. The antibacterial effects of the BC/Ag composite powders against Pseudomonas aeruginosa and Staphylococcus aureus were assessed from the minimum inhibitory concentrations (MICs) and minimum bactericidal concentrations (MBCs) method, and an excellent antibacterial performance was discovered.     

Antibacterial Effects of Silver Doped Polyethyleneglycol Based Polyamidoamine Side Chain Dendritic Polyurethane

Antibacterial activity was imparted with polyamidoamine (PAMAM) side chain dendritic polyurethane (SCDPU‐PEG) by doping of silver particles. Antibacterial activities of both the polyurethane (SCDPU‐PEG) and its silver doped structures were investigated against Escherichia coli bacteria. The silver doped polymeric structures were found to exhibit antibacterial activity while the polymer without silver loading showed no antibacterial activity. Formation of silver doped side chain dendritic polymers was investigated from the UV‐vis plasmon absorption band of silver particles.     

Fabrication and superhydrophobic behavior of fluorinated microspheres

We describe the preparation of fluorinated microspheres by precipitation polymerization and their use to fabricate superhydrophobic surfaces. For that purpose, two different approaches have been employed. In the first approach, a fluorinated monomer (either 4-fluorostyrene or 2,3,4,5,6-pentafluorostyrene) was added to the initial mixture of monomers constituted by styrene (S) and divinylbenzene (DVB). The second approach is based on the encapsulation of a block copolymer, polystyrene-b-poly(2,3,4,5,6-pentafluorostyrene), during the polymerization of the monomers (S and DVB), thus enabling the formation of particles with perfluorinated chains instead of single functional groups at the interface. Both approaches led to narrow polydisperse particles with fluoro-functional groups at the interface as demonstrated by scanning electron microscopy (SEM), infrared (IR) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Surface array of particles obtained by simple solvent casting presented superhydrophobic behavior with contact angles of water droplets of ca. 160-165°.     

Polystyrene–Polyperfluorooctylethyl acrylate Diblock Copolymers: The Effect of Dilution of the Fluorinated Mesogenic Chains on Bulk and Surface Properties

Summary : Three smectic poly(styrene-b-perfluorooctylethyl acrylate) block copolymers (S-b-AF8) with different degrees of polymerization (n, m) of the relative blocks were synthesized by atom transfer radical polymerization (S, n = 25; AF8 m = 2, 6, 23). The mesophase structure and transition temperatures were investigated by DSC and WAXD. The block copolymer having the shortest fluorinated block was blended with a thermoplastic elastomer SEBS in different proportions, in order to look at the effect of a further dilution of the perfluorinated groups on non-wetting properties. Thin films of the block copolymers as well as the blends exhibited large contact angles with both water and n-hexadecane, which resulted in low solid surface tensions. XPS findings at different photoemission angles confirmed the effective surface segregation of the mesogenic chains of the fluorinated polymer block.     

Composite Polyaniline/MF-4SK Membranes: A Chemical Template Synthesis and the Sorption and Conduction Properties

The sorption and hydrophilic properties of composite membranes PAN/MF-4SK, obtained by a chemical template synthesis, are studied. The synthesis is performed in static and dynamic conditions for perfluorinated sulfo-cationite membranes MF-4SK in 0.01 M aniline solutions in 0.5 M H₂SO₄ and 0.01 M FeCl₃ in 0.5 M H₂SO₄. The aniline sorption and polymerization kinetics is studied by conductimetry, radioisotope, and optical methods. The polymerization rate is found to depend on the oxidant concentration and the sequence of the membrane saturation with aniline. An increase in the intensity of the color of a composite film, which depends on the balance between the quinoimine, amine, and radical-cation fragments in the perfluorinated matrix, does not lead to any substantial changes in the moisture content or the ac electroconductivity. Implanting polyaniline chains into the perfluorinated matrix presumably leads to a molecular reorganization of water at the expense of a change in its association at the point where redox fragments of polyaniline converge with side segments of the template matrix.     

Silicone composites containing stabilized silver clusters or nanoparticles

Silver nanoparticles are of high importance due to their electrical, magnetic, and optical properties, as well as catalytic and biocidal activity that are superior to the bulk silver and other metals. To prepare certain devices, generally, silver is incorporated into a matrix either as preformed or in situ‐generated particles. Silver nanoparticles were generated in situ into a silicone matrix formed by cohydrolysis of the mixture of silanes, each of them having a certain role: dimethyldiethoxysilane (DMDES) as a precursor for highly flexible polydimethylsiloxane, methyltriethoxysilane (MTES) as a cross‐linker highly compatible with polydimethylsiloxane, and 3‐aminopropyltriethoxysilane as a stabilizer, since it can readily complex to silver atoms through its amine functionality. Dimethylformamide (DMF) was used as a solvent for the silver nitrate and reducing agent. The samples were investigated both in sol state and as aged coating films deposited on glass substrate. The complexation of the silver and the matrix formation were emphasized by FTIR. The size of the formed silicone particles encapsulating silver was estimated by dynamic light scattering (DLS) (about 100 nm) in sol and by AFM in film (about 90 nm). The formation of the clusters or nanoparticles depending on the ratio between the reducing and complexing agents was evidenced by UV–Vis absorption spectra. Thus, it would create conditions to stop and isolate clusters at the desired size by precise control of the experimental conditions. The composites could be used alone as antibacterial‐coating materials but also, porous silica having incorporated silver clusters with potential applicability in catalysis may result after their calcination. Copyright © 2010 John Wiley & Sons, Ltd.     

Hydroxyl functional polyester dendrimers as stabilizing agent for preparation of colloidal silver particles—a study in respect to antimicrobial properties and toxicity against human cells

The presented study concerns the preparation and investigation of silver particles in presence of hydroxylated polyester dendrimers used as stabilizing agent. Altogether a full series of water soluble and aliphatic bis-MPA dendrimers from first to fifth generation was used as to stabilize silver nanoparticles in situ. A special focus is set on the biological properties. The antibacterial properties of the dendrimer stabilized silver particles are tested against Escherichia coli and the toxicity against human cells is tested with the human epithelial cell line A549. Under the chosen testing arrangement, it was observed that the silver particles contain a significant antibacterial effect against E. coli. Silver particles stabilized in situ with dendrimers of higher generation seem to contain a stronger antibacterial property. No toxicity against human cells was observed for the silver particles even in case of the highest investigated silver concentration. Altogether the here prepared and investigated silver particles could offer a great potential for application as antibacterial agent with low human toxicity.     

Preparation of novel methyl methacrylate/fluorinated silsesquioxane copolymer film with low surface energy

Random copolymers of methyl methacrylate and fluorinated polyhedral oligomeric silsesquioxane (F-POSS) were synthesized and the corresponding thin films were prepared from solvent casting. Their microstructure was confirmed by ¹H NMR, elemental analysis and GPC. Separation occurs in the bulk of the film during solvent evaporation which can be evidenced by Transmission Electron Microscopy, TEM, with POSS-rich nanophase sizes from 20 to 50 nm. Nanostructuration is attributed to the self-assembly of F-POSS due to the cluster-cluster interactions resulting from the nature of their ligands, i.e., cycloaliphatic ligands and perfluorinated chains. Thermogravimetric analysis was used to investigate the thermal degradation temperature. It was shown that when F-POSS content is higher than 2.8 mol%, the incorporation of F-POSS could improve the thermal stability of PMMA significantly. In addition, it was shown that these fluorinated POSS-based copolymer surfaces could reduce the surface energy and could be used to design water-repellant nanocomposite coatings.

     

Formation of mesophases by fluorinated enaminoketone Ni(II), Cu(II) and VO(II) complexes

Mesogenic tetradentate cis-enaminoketone Ni(II), Cu(II) and VO(II) complexes with rod-like and disc-like molecular shapes were synthesized. In these compounds some of the alkyl chains were perfluorinated. Replacing the alkyl chains by fluorinated chains stabilizes the columnar hexagonal Col_h phase whereas lamellar phases are destroyed.     

Side chain polysiloxanes with fluorinated mesogenic groups. The role of the fluorine content on the properties of the smectic A state

A series of liquid crystalline polymers has been synthesized in which fluorinated or semi-fluorinated mesogenic moieties are used as side groups linked to a polysiloxane backbone. Clear-cut differences in the structure of the smectic A phase are evidenced between fluorinated polymers and their classical non-fluorinated homologues. In a comparative analysis, we discuss the relevance of the steric hindrance of perfluorinated sequences and of the microsegregation of the backbone in response to these modifications as related to the fluorine content in the side group and to the proportion of mesogenic groups.     

Design of super-tough and antibacterial PPR/nano-ZnO composites based on the excellent dispersion of ZnO particles

Herein, polyvinyl pyrrolidone (PVP) dispersants are used to disperse and isolate zinc oxide (ZnO) particles. A high-pressure spray device is used to dry the dispersed nano-fillers quickly to achieve the structure of PVP chains wrapping and isolating ZnO particles. Scanning electron microscopy shows that most of the size of the agglomerated ZnO nanoparticles in polypropylene random (PPR, obtained by random copolymerization of propylene and ethylene) is maintained below 100 nm, and only a small amount of large agglomerates with a particle size less than 400 nm. An excellent dispersion of nano-ZnO fillers prepared by this method can greatly improve the toughness of PPR and endow it with good antibacterial properties. When the content of the ZnO nanoparticles is 3 wt%, the notched impact strength of PVZ3 increases to 48.85 kJ m⁻² (unbroken), which is 3.6 times than that of pure PPR. In addition, 3 phr ZnO nanoparticles give PPR excellent antibacterial properties, with an antibacterial rate of 99.9% (Escherichia coli and Staphylococcus aureus). The value of antibacterial activity (E. coli) of PVZ3 reached more than 6.0, which is nearly three times that of PZ.     

Tunning Silver@Gold core@shell incorporated in poly (vinyl alcohol) via laser ablation: Antibacterial activity and cell viability behavior for wound healing

This study aims to bio-modulate Poly (vinyl alcohol) crosslinked by silver and gold nanoparticles fabricated by one-step laser ablation. The optical, cell viability, and antibacterial characterization of the fabricated films have been studied via different techniques. FTIR and XRD were used to investigate the molecular structures of the polymer matrix of Polyvinyl Alcohol incorporating gold and silver (Ag-Au NPs) created by laser ablation. XRD data illustrate the semicrystalline structure of PVA, with two hump peaks at 2θ = 8.52° and 2θ = 20.17° that are decreased when loaded with Ag-Au nanoparticles at different laser ablation times. The FT-IR spectra demonstrated a variation in the intensity of different peaks compared to the spectrum of the Polyvinyl Alcohol. This suggests that PVA and Ag-Au nanoparticles interacted and complexed in semicrystalline areas. The optical energy gap (Eg) reduces from 5.55 eV to 5.00 eV during direct transition and from 4.79 eV to 3.10 eV during indirect transition. The cell viability value for sample S2 was 91.7 ± 5.8%, indicating that both nanocomposites are biocompatible. S2 represents the high values of the inhibition zone, which make it preferred in antibacterial applications. The results demonstrate that Polyvinyl Alcohol/metal composite materials have excellent cell viability and antibacterial properties, implying that they may be suggested in antibacterial utilizations.     

Correlated layer structures: a novel type of liquid crystalline phase with 2D-lattice

A novel liquid crystalline quaternary five-block molecule is reported which is composed of four incompatible molecular parts, a rigid biphenyl core, two polar 2,3-dihydroxypropoxy groups in the terminal 4- and 4'-positions, and a branched semiperfluorinated chain in the lateral 3-position, consisting of a perfluorinated and a lipophilic hydrocarbon wing. The self-organization of this compound was studied by polarized light optical microscopy, differential scanning calorimetry, and X-ray diffraction of aligned samples. These investigations confirm a novel liquid crystalline phase with two-dimensional (2D) lattice (columnar mesophase), which results from the positional correlation of smectic layers. The layer structure results from the segregation of the bolaamphiphilic parts from the side chains. Within the aromatic sublayers the biphenyl cores are arranged parallel to the layer planes, and the hydrogen-bonding networks of the terminal diol groups are segregated from the biphenyl cores, forming separate columns. The correlation between adjacent layers is due to the (partial) segregation of the fluorinated and hydrogenated parts of the lateral chains in the nonpolar sublayers.     

Preparation and characterization of polyacrylamide–silver nanocomposites

Polyacrylamide–silver nanocomposites are successfully prepared by irradiating the aqueous solution of AgNO₃ and acrylamide monomer with ⁶⁰Co γ-ray. The composites are found to contain nanometer silver particles with a narrow size distribution and a homogeneous dispersion. The existing of isopropanol (as a hydroxyl radical scavenger and chain transfer agent) in system affects the properties of both the dispersed phase and matrix of the nanocomposites. The fast-formed polymer chains probably play a key role in preventing the aggregation of silver particles which are reduced later.