Polypyrrole-coated poly(vinyl chloride) powder particles: surface chemical and morphological characterisation by means of X-ray photoelectron spectroscopy and scanning electron microscopy

Polypyrrole (PPy)-coated poly(vinyl chloride) (PVC) powder particles were prepared by the in situ chemical polymerisation of pyrrole in aqueous solutions in the presence of PVC powder particles. The PVC particles in suspension served as a hydrophobic substrate for the in situ polymerisation of pyrrole using iron chloride as the oxidising agent and sodium p-toluene sulfonate. In these conditions, tosylate-doped PPy (PPyTS) was obtained and chlorides were inserted as minor codoping species. In some cases, the pyrrole was polymerised after incubating the PVC particles with poly(N-vinyl pyrrolidone). Scanning electron microscope (SEM) micrographs showed that the PVC particles retained their initial, quasispherical shape after coating by PPy. At low magnification, the coated PVC particles appeared smooth, but at high magnification, they exhibited a decoration by elementary nanoparticles of about 200-nm size due to PPy bulk powder grains. Elemental analysis indicated a mass loading of PPy in the range 1–58% w/w. Specific surface analysis by X-ray photoelectron spectroscopy (XPS) resulted in the spectra of the PPy-coated PVC particles resembling those of bulk powder PPyTS even for low PPy mass loading. The surface fraction of PPy repeat units was found to vary in the 55–91% range. This result is consistent with the SEM observation of the PPy nanoparticles at the surface of PVC powder grains. However, despite the important loading of PPy, the XPS estimation of the overlayer thickness is in favour of a patchy coating rather than continuous coatings of PPy.     

自支撑柔性氮掺杂碳织物电极的制备与性能研究

本文以纯棉织物为基底,吡咯单体为氮源,采用简单的原位聚合-高温煅烧的方法制备了自支撑柔性氮掺杂织物（N-CT）. 利用傅立叶红外技术、X射线光电子能谱、比表面积测试、扫描电子显微镜对所得产物进行结构与形貌表征. 结果表明,碳化后聚吡咯主要以纳米碳球包覆在碳织物表面,N-CT电极的比表面积为495.0 m²·g^-1,其含氮量为2.26%. 电化学测试表明,在0.5 A·g^-1的电流密度下N-CT电极的比电容器为256.2 F·g^-1,经过5000次的恒流充放电循环后电容保持率为98.3%,库伦效率保持率在98.8%左右,具有良好的柔性和机械性能.     

Surface free energy and bacterial retention to saliva-coated dental implant materials--an in vitro study

The aim of the present investigation was to compare the in vitro bacterial retention on saliva-coated implant materials (pure titanium grade 2 (cp-Ti) and a titanium alloy (Ti–6Al–4V) surfaces), presenting similar surface roughness, and to assess the influence of physico-chemical surface properties of bacterial strain and implant materials on in vitro bacterial adherence. Two bacterial strains (one hydrophilic strain and one hydrophobic strain) were used and the following were evaluated: bacterial cell adherence, SFE values as well as the Lifshitz-van-der Waals, the Lewis acid base components of SFE, the interfacial free energy and the non-dispersive interactions according to two complementary contact angle measurement methods: the sessile drop method and the captive bubble method.

Our results showed similar patterns of adherent bacterial cells on saliva-coated cp-Ti and saliva-coated Ti–6Al–4V. These findings could suggest that bacterial colonization (i.e. plaque formation) is similar on saliva-coated cp-Ti and Ti–6Al–4V surfaces and indicate that both materials could be suitable for use as transgingival abutment or healing implant components. The same physico-chemical properties exhibited by saliva-coated cp-Ti and TA6V, as shown by the sessile drop method and the captive bubble method, could explain this similar bacterial colonisation. Therefore, higher values of total surface free energy of saliva-coated cp-Ti and saliva-coated TA6V samples (γ_SV ≈65 mJ/m²) were reported using the captive bubble method indicating a less hydrophobic character of these surfaces than with the sessile drop method (γ_S ≈44.50 mJ/m²) and consequently possible differences in oral bacterial retention according the theory described by Absolom et al.

The number of adherent hydrophobic S. sanguinis cells was two-fold higher than that of hydrophilic S. constellatus cells. Our results confirm that physico-chemical surface properties of oral bacterial strains play a role in bacterial retention to implant materials in the presence of adsorbed salivary proteins.     

可快速充放电聚吡咯/碳纳米管复合材料电化学聚合与表征

采用恒电流法制备了具有可快速充放电性能的对甲基苯磺酸根(TOS-)掺杂聚吡咯/功能化单壁碳纳米管(PPy-TOS/F-SWNTs)复合材料,扫描电镜(SEM)结果表明该复合材料呈纳米棒状构成的多孔结构,棒径约为70nm;比表面积(BET)测试分析表明该复合材料有着较高的比表面积(12.64m2.g-1)和大的介孔孔隙率(20-40nm).循环伏安(CV)、电化学阻抗谱(EIS)和恒电流充放电(GC)电化学分析表明该材料具有优异的快速充放电性能,在800mV的电位窗和2.5A.g-1(功率密度为2kW.kg-1)的电流密度下该材料具有211F.g-1的比容量(能量密度为18.7Wh.kg-1),而当充放电电流高达80A.g-1(功率密度为60kW.kg-1)时比容量仍可达141.8F.g-1(能量密度为12.6Wh.kg-1),同时该材料还表现出优异的稳定性,在10A.g-1大电流下经历10000圈循环后容量仍保持95.2%.     

Adsorption and activity of Thermomyces lanuginosus lipase on hydrophobic and hydrophilic surfaces measured with dual polarization interferometry (DPI) and confocal microscopy

The adsorption and activity of Thermomyces lanuginosus lipase (TLL) was measured with dual polarization interferometry (DPI) and confocal microscopy at a hydrophilic and hydrophobic surface. In the adsorption isotherms, it was evident that TLL both had higher affinity for the hydrophobic surface and adsorbed to a higher adsorbed amount (1.90 mg/m²) compared to the hydrophilic surface (1.40–1.50 mg/m²). The thickness of the adsorbed layer was constant (3.5 nm) on both surfaces at an adsorbed amount >1.0 mg/m², but decreased on the hydrophilic surface at lower surface coverage, which might be explained by partially unfolding of the TLL structure. However, a linear dependence of the refractive index of the adsorbed layer on adsorbed amount of TLL on C18 surfaces indicated that the structure of TLL was similar at low and high surface coverage. The activity of adsorbed TLL was measured towards carboxyfluorescein diacetate (CFDA) in solution, which upon lipase activity formed a fluorescent product. The surface fluorescence intensity increase was measured in a confocal microscope as a function of time after lipase adsorption. It was evident that TLL was more active on the hydrophilic surface, which suggested that a larger fraction of adsorbed TLL molecules were oriented with the active site facing the solution compared to the hydrophobic surface. Moreover, most of the activity remained when the TLL surface coverage decreased. Earlier reports on TLL surface mobility on the same surfaces have found that the lateral diffusion was highest on hydrophilic surfaces and at low surface coverage of TLL. Hence, a high lateral mobility might lead to a longer exposure time of the active site towards solution, thereby increasing the activity against a water-soluble substrate.     

Enhanced nucleation, smoothness and conformality of ultrananocrystalline diamond (UNCD) ultrathin films via tungsten interlayers

Extremely smooth (6 nm RMS roughness over 4 μm²), thin (100 nm), and continuous ultrananocrystalline diamond (UNCD) films were synthesized by microwave plasma chemical vapor deposition using a 10 nm tungsten (W) interlayer between the silicon substrate and the diamond film. These UNCD films possess a high content of sp³-bonded carbon. The W interlayer significantly increased the initial diamond nucleation density, thereby lowering the surface roughness, eliminating interfacial voids, and allowing thinner UNCD films to be grown. This structural optimization enhances the films’ properties and enables its integration with a wide variety of substrate materials.     

Synthesis and characterization of nanosilica prepared by precipitation method

Nanosilica was prepared by precipitation method and was characterized by various analytical tools. From transmission electron micrograph the silica particles are found to have almost spherical shape with a dimension of 50 nm. The surface area is found to be of 560 m² g⁻¹ and density 2.2 g cm⁻³. From thermogravimetric analysis the total silanol density in the silica is found to be 7.68 nm⁻². A two tier hydration model is proposed from the results of thermogravimetric analysis. The number of reactive silanols that forms hydrogen bond with water molecules is found to be 2.48. The infrared spectral data supports the presence of hydrogen bonded silanol group and the siloxane groups in silica.     

Electrolysis of sodium chloride using composite poly(styrene-co-divinylbenzene) cation exchange membranes

Composite cation exchange membranes are prepared from cross-linked styrene-divinylbenzene copolymers for the electrolysis of sodium chloride to produce sodium hydroxide and chlorine by selective removal of sodium ions. It is prepared from a syrup of the polymer using dual initiating system and is modified with chloroacetic acid to introduce acid functional groups (COO⁻) on its surface. The effect of the modification is confirmed by FTIR, SEM, contact angle, water content, and ion exchange capacity measurements. The performance of the membrane has been evaluated in terms of current efficiency and power consumption and the effect of current density, salt concentration and flow rate on efficiency has been studied. Our membrane has an ion exchange capacity of 0.833 meq./g which is close to that of the commercially available Nafion-117 membrane having an ion exchange capacity 0.9 meq./g. The Nafion-117 used for electrodialysis of sodium sulfate has a current efficiency of around 90% and specific energy consumption of 0.1 kW/mol at 2N concentration of the salt at 1000 A/m². Our membrane used for electrodialysis of sodium chloride has a current efficiency of 93% and a power consumption of around 0.3122 kW/mol at the same concentration of salt and at a current density of 254 A/m². The two-dimensional space-charge model in cylindrical coordinates has been solved semi-analytically to obtain the effective wall potential and pore size of the membrane which are difficult to measure directly. The experimentally obtained solute flux and current density have been fitted to the model and optimum values of effective wall potential and pore diameter have been determined to be 98.5 mV and 0.8 nm, respectively.     

Preparation and Properties of Magnetic-fluorescent Microporous Polymer Microspheres

Microporous microspheres can be used as functional nanomaterial carriers for their microporous structure and higher specific surface area. In this study, magnetic fluorescent polymer microspheres were prepared by incorporating Fe₃O₄ nanoparticles and CdSe/ZnS quantum dots(QDs) into hyper-crosslinked microporous polymer microspheres(HCMPs) via the in situ coprecipitation method and swelling-diffusion. The HCMPs predominantly have micropores, and their specific surface area is as high as 703.4 m²/g. The magnetic-fluorescent microspheres maintain the superparamagnetic behavior of Fe₃O₄, and the saturation magnetization reaches 38.6 A·m²/kg. Moreover, the composite microspheres exhibit an intense emission peak at 530 nm and achieve good fluorescence.     

AFM study of conducting polymer polypyrrole nanoparticles formed by redox enzyme - glucose oxidase - initiated polymerisation

Redox enzyme – glucose oxidase E.C. 1.1.3.4 from Penecillum vitale (GOx) – initiated polypyrrole (Ppy) synthesis was applied for the formation of polypyrrole based nanoparticles. The increase in optical absorbance at λ = 460 nm was exploited for the monitoring of polypyrrole polymerisation process. The shape and size of the formed Ppy nanoparticles was also monitored by means of contact mode AFM. The highest increase in the diameter of the formed Ppy nanoparticles was detected during 15-day period. AFM imaging was performed in contact mode to investigate the shape and flexibility of particles deposited on the SiO₂ and Pt surfaces. Contact mode AFM investigations allowed us to conclude that after drying at 50 °C the formed Ppy particles are more flexibly deposited on the Pt electrode if compared to those deposited on the SiO₂ substrate. The application of well-shaped Ppy nanoparticles in biomedicine, chromatography and bioanalysis may be predicted.     

Pd基无涂层整体式催化剂上甲苯催化燃烧净化研究

采用化学镀法在堇青石蜂窝陶瓷基体上制备了Pd基无涂层整体式催化剂Pd/cord,并对其在甲苯催化燃烧净化反应中的催化性能进行了研究.结果表明,Pd/cord催化剂在钯负载量较低(如为0.24％)时,即可使甲苯从201℃起燃后,突跃到226℃完全转化,表现出良好的甲苯催化燃烧净化性能.该类催化剂在空速6000h-1 ～4...     

NEXAFS study of a Pt-containing rod-like organometallic polymer (Pt-DEBP): molecular orientation onto HOPG, Au/Si(1 1 1), Cr/Si(1 1 1) and Si(1 1 1) surfaces

The influence of different substrates on the molecular orientation of organometallic polymer Pt-DEBP, [Pt(PBu₃)₂CCC₁₂H₈CC]_n, has been investigated by NEXAFS spectroscopy. Thin films were deposited on HOPG, Au/Si(1 1 1), Cr/Si(1 1 1), Si(1 1 1) and stainless steel. The assignment of the spectral features has been carried out on the basis of previous STEX calculations performed on phenylacetylene model molecule in gas phase and adsorbed on Pt(1 1 1) and Cu(1 0 0). Angular dependent analysis of the π* resonance occurring at 285.50 eV photon energy deriving by the benzene carbon orbitals showed a polarisation effect for all substrates. A preferential molecular orientation at nearly 40° to the surface normal was observed. This result might be explained by the strong interaction between sp and sp² carbons of the organic diethynylbiphenyl DEBP moiety contained in close chains, leading to polymer self-assembling.     

Molecular dynamics study of homogeneous nucleation in supercooled clusters of sodium bromide

Molecular dynamics simulations are carried out on clusters comprised of 108, 256, 500, and 864 Na⁺Br⁻ ion pairs represented by a Born–Mayer–Hugins interaction potential. Clusters with free boundaries are chosen in order to avoid the interference with nucleation caused by periodic boundary conditions. The melting point increases with increasing size of cluster as expected. The nucleation has been found to start near the surface of a NaBr cluster. The rates of nucleation in melted clusters are estimated based on classical nucleation theory. The interfacial free energies of 73.3–76.4 mJ/m² in temperature range of 400–550 K derived from kinetics of freezing are in the same order of magnitude as those predicted by Turnbull's relation and Buckle and Ubbelohde's observation. Sizes of critical nuclei are inferred from classical expressions and Voronoi polyhedra analyses.     

微/纳米ZnO绒球的制备及其在自然光下催化降解有机染料性能

以谷氨酸氟硼酸(GluBF₄)离子液体水溶液为反应介质,以物质的量比为1:6的二水合醋酸锌[Zn(Ac)₂·2H₂O]和氢氧化钠为原料,室温下制备前驱体,再微波辅助加热制备了纳米氧化锌粉体,获得了纳米结构微米尺寸纳米ZnO绒球.利用场发射扫描电镜(FESEM)、X射线衍射(XRD)、比表面(BET)、能量色散谱(EDS)等对产物进行了表征.所得产物为六方晶系纤锌矿结构,粉体粒径20.4 nm,绒球比表面积为28.3 m²·g^-1,产物纯度较高,收率95.3%.同时探讨了纳米ZnO绒球生成的可能机理.该纳米材料在日光下显示较高的光催化活性和稳定性.分别配制浓度为10 mg·L^-1的100 mL甲基橙(MO)和甲基紫(MV)水溶液, 30 mg纳米氧化锌为光催化降解催化剂,太阳光激发下5 h脱色率分别达到74.3%和96.9%;溶液总有机碳(TOC)含量随光降解的进行缓慢下降;光催化剂重复利用5次,催化剂形貌不变、颜色不变,质量基本未发生变化.     

Chelating ionophore based membrane sensors for copper(II) ions

Acetylacetone, ethylacetoacetate and salicyldehyde, are reported to form chelates with copper of high stability as compared to other metals. Therefore, PVC based membranes of bis[acetylacetonato] Cu(II) (A), bis[ethylacetoacetate] Cu(II) (B) and bis[salicyldehyde] Cu(II) (C) have been investigated as copper(II) selective sensors. The addition of sodium tetraphenylborate and various plasticizers, viz., DOS, TEHP, DOP, DBP and TBP have been found to substantially improve the performance of the sensors. The membranes of various compositions of the three chelates were investigated and it was found that the best performance was obtained for the membrane of composition A (1%): PVC (33%): TBP (65%): NaTPB (1%). The sensor shows a linear potential response to Cu(II) over wide concentration range 2.0 × 10⁻⁶ to 1.0 × 10⁻¹ M (detection limit 0.1 ppm) with Nernstian compliance (29.3 mV decade⁻¹ of activity) between pH 2.6 and 6.0 with a fast response time of 9 s. The potentiometric selectivity coefficient values as determined by match potential method (MPM) indicate excellent selectivity for Cu²⁺ ions over interfering cations. The sensor exhibits adequate shelf life (3 months) with good reproducibility (S.D. ±0.2 mV). The sensor has been used in the potentiometric titration of Cu²⁺ with EDTA. The utility of the sensor has been tested by determining copper in vegetable foliar and multivitamin capsule successfully.     

Effect of monascus pigment derivatives on the electrophoretic mobility of bacteria, and the cell adsorption and antibacterial activities of pigments

Various amino acid derivatives of monascus pigments were synthesized. The effects of pigment derivatives on the pigment adsorption ratio, electrophoretic mobility (EPM) of bacterial cells, and antibacterial activity were investigated under varying conditions of pigment type, pigment concentration, pH, and ionic strength. Two hydrophobic and two hydrophilic derivatives were selected as model pigments. There was a close relationship between the antimicrobial activity and the pigment adsorption ratio. Against Escherichia coli, the hydrophobic l-Tyr and l-Phe derivatives (log P = 3.18 and 3.57) exhibited high antimicrobial activities (MIC = 8 and 16 mg/L) and high cellular adsorption ratios (9.6 and 10.9 mg/L). The hydrophilic l-Glu and l-Asn derivatives (log P = 1.40 and 0.47) exhibited low activities (MIC = 64 and 128 mg/L) and low adsorption ratios (4.7 and 4.0 mg/L). The electrophoretic mobility of 11 different bacteria varied between −1.93 × 10⁻⁸ and −1.19 × 10⁻⁸ m² V⁻¹ s⁻¹ regardless of Gram⁺ or Gram⁻. The l-Phe derivative showed low MIC values (high antimicrobial activities) against bacteria with a high electrophoretic mobility. A positive linearity between the pigment adsorption ratio and the electrophoretic mobility was established. When the four pigment derivatives were added to E. coli solutions, the electrophoretic mobility of cells in all cases sharply increased with an increasing pigment concentration. The mobility value was high for hydrophobic pigment derivatives in descending order of l-Phe (0.8 × 10⁻⁸ m² V⁻¹ s⁻¹), l-Tyr (0.68 × 10⁻⁸ m² V⁻¹ s⁻¹), l-Glu (0.46 × 10⁻⁸ m² V⁻¹ s⁻¹), and l-Asn (0.44 × 10⁻⁸ m² V⁻¹ s⁻¹). Additional adsorption of the hydrophobic derivatives probably occurred due to a hydrophobic interaction between the pigment and the pigment-coated cells. The electrophoretic mobility decreased gradually with an increasing pH and/or ionic strength with both addition and no addition of the pigment derivatives. The pattern of change of the pigment adsorption ratio under varying pH and/or ionic strength values was similar to the pattern for electrophoretic mobility.     

Synthesis of γ-Al2O3 with High Surface Area and Large Pore Volume by Reverse Precipitation-azeotropic Distillation Method

γ-Al₂O₃ with high surface area and large pore volume combined with high thermal stability was synthesized by a reverse precipitation-azeotropic distillation method. The effects of azeotropic distillation on the characteristics of γ-Al₂O₃ were studied by means of X-ray diffraction(XRD), Fourier transform infrared(FTIR) spectroscopy, transmission electron microscopy(TEM) and N₂ adsorption-desorption. The results show that γ-Al₂O₃ dried by azeotropic distillation has excellent structure characteristics with a high surface area of 426 m²/g and a large pore volume of 2.56 cm³/g. After calcination at 1100℃, the surface area of γ-Al₂O₃ was still 92 m²/g with a large pore volume of 1.00 cm³/g, indicating the potential application in catalyst and petroleum industry.     

Plasticizer-free microspheres for ionophore-based sensing and extraction based on a methyl methacrylate-decyl methacrylate copolymer matrix

Plasticizer-free methyl methacrylate-decyl methacrylate (MMA-DMA) microspheres were prepared under mild, non-reactive conditions using a high-throughput particle generator. The particles were perfectly smooth and monodisperse, with a particle diameter of approximately 10.0 μm. In order to evaluate the suitability of the polymer as a matrix for bulk extraction processes, lipophilic sensing components were incorporated into the particles. Particles contained either a H⁺-selective chromoionophore (ETH 5294) only (type 1), or a K⁺-selective ionophore (BME-44), anionic sites (NaTFPB), and ETH 5294 (type 2). Type 1 particles responded according to an anion–proton coextraction mechanism and demonstrated Hofmeister selectivity by showing a preference for more lipophilic sample anions (ClO₄⁻>NO₃⁻>Cl⁻). Particles of type 2 functioned by way of an ion-exchange equilibrium and demonstrated a functional response for K⁺, with a dynamic range from 10⁻¹–10⁻⁴ M K⁺. These particles also exhibited selectivity comparable to that previously reported for analogous particles made from bis(2-ethylhexyl sebacate) (DOS)-plasticized poly(vinyl chloride) (PVC) and DMA-DOS. In addition, the behavior of both types1 and 2 particles was in agreement with analogous thin film optical sensors (optodes) prepared from MMA-DMA. With the advent of ionophore-based plasticizer-free microspheres a wide variety of ions may potentially be assessed using various popular bead-based sensing strategies, such as lab-on-a-chip technologies, bundled optical fiber arrays, and flow cytometry, without experiencing the deleterious effects resultant of plasticizer leaching.     

Design of polymeric microparticles with improved structural properties: Influence of ethylstyrene monomer and of high proportions of crosslinker

Macroreticular poly(styrene-co-divinylbenzene) microparticles with high proportions of divinylbenzene have been synthesized and the effects of the operating conditions and of the proportion of ethylstyrene, which is the monomer accompanying divinylbenzene in commercial divinylbenzene, on the structural characteristics of the microparticles have been investigated. The use of commercial divinylbenzene with a purity of 80% enabled the synthesis of microparticles with a high grade of crosslinking, which showed enhanced structural properties, such as BET specific surface areas (some types of particles reached more than 500 m² g⁻¹) or pore volumes (mesopore volumes higher than 0.7 cm³ g⁻¹, and macropore volumes higher than 0.5 cm³ g⁻¹). At the same time, microparticles with the same percentage of divinylbenzene but a different percentage of ethylstyrene were synthesized by using, as raw material, two types of commercial divinylbenzene with purities of 80% and 55%, respectively. Comparison of the properties of both these types of particle indicated that ethylstyrene has a significant effect on macropore volume in the case of the lowest proportion of porogen in the synthesis mixture, within the range of values investigated.