Mineralization of single flexible polyelectrolyte molecules

Conformation of a single flexible polyelectrolyte molecule with a hydrophobic backbone in aqueous solution is effected by the interplay of the short-range intramolecular attraction and the long-range Coulomb repulsion. The conformation can be frozen if the molecule is trapped by a solid substrate. With this approach, we prepared the range of single molecule templates from poly(2-vinylpyridine) (P2VP) deposited on the surface of Si-wafer or mica in different conformations from an elongated wormlike coil to compact globule. Pd(+2) was coordinated by P2VP via an ion exchange reaction exposing the samples to palladium acetate acidic aqueous solution. In the next step, Pd(+2) was reduced by dimethylamine borane. This route results in wire-shaped metallic nanoparticle assembles of about 2-5 nm in diameter and 50-700 nm in length. The conformation and size of the underlaying polyelectrolyte molecules determine the dimensions of nanoparticles.     

Highly carbonized polyaniline micro- and nanotubes

We have obtained unique highly carbonized polyaniline micro- and nanotubes as a new, thermally stable nanomaterial for nanosensors and nanodevices with a wide range of possible applications, comparable to carbon nanotubes. Polyaniline nanostructures are easy to prepare and handle in wet conditions, including controlled growth. Temperature-induced transformations of polyaniline micro- and nanotubes into highly carbonized analogues have been observed at and above 800 °C, while the temperature was elevated slowly from 20 °C up to 1100 °C. Carbonized products have the same morphology (micro- and nanotubes), but a lower spin density than the starting material (e.g. 10¹⁴ g⁻¹ for the sample heated at and above 800 °C, and 10¹⁹ g⁻¹ before heating). Simultaneously, the electrical conductivity changes from 7.4 × 10⁻⁵ S/cm for the starting material to 4.8 × 10⁻⁹ S/cm, 1.3 × 10⁻¹¹ S/cm and finally 2.4 × 10⁻⁶ S/cm for samples obtained at room temperature, 250 °C, 500 °C and 800 °C, respectively. Chemical transformations and unique molecular structures formed are discussed. Applications in nanotechnology, including sensors and electronic nanodevices, are expected in the light of experiments already performed.     

Highly reversible and multi-stage cantilever actuation driven by polyelectrolyte brushes

Microcantilever bending can be reversibly driven by conformational changes of phosphate containing polyelectrolyte brushes when exposed to different pH or salt solutions. The deflection of the cantilevers allows a detailed analysis of the properties of polymer brushes, while these systems are also a first step toward polymer-based nanoactuators.     

Hydrothermal-induced structure transformation of polyelectrolyte multilayers: from nanotubes to capsules

The assembled polyelectrolyte nanotubes composed of poly(styrenesulfonate) and poly(allylamine hydrochloride) multilayers by using the layer-by-layer assembly combined with the porous template method can be transformed into capsules by a high-temperature treatment. Scanning electron microscopy and confocal laser scanning microscopy images revealed the whole transition process. The structure transformation of polyelectrolyte multilayers after annealing can be initiated by the input of thermal energy which leads to a breakage of ion pairs between oppositely charged polyelectrolyte groups. The transition process from tubes to capsules is supposed to be driven by the Raleigh instability and leads to the generated polyelectrolyte capsules with different sizes.     

Persistence length control of the polyelectrolyte layer-by-layer self-assembly on carbon nanotubes

We have studied layer-by-layer polyelectrolyte self-assembly on pristine individual single-wall carbon nanotubes as a function of solution ionic strength. We report the existence of an ionic strength threshold for the deposition, below which the majority of nanotubes remain uncoated. Once the ionic strength reaches the threshold value, the majority of the individual nanotubes become coated with polyelectrolytes. Our results indicate that the self-assembly process likely involves wrapping of polymer chains around nanotubes and that the polymer chain's ability to bend in order to accommodate the nanotube curvature is one of the critical parameters controlling layer-by-layer electrostatic self-assembly on these one-dimensional templates.     

Highly sensitive and fast responsive fiber-optic modal interferometric pH sensor based on polyelectrolyte complex and polyelectrolyte self-assembled nanocoating

A new fiber-optic pH sensor is demonstrated by coating negatively charged polyelectrolyte complex (PEC⁻) nanoparticles, made of sodium carboxymethyl cellulose and poly(diallyldimethylammonium chloride) (PDDA), and positively charged PDDA on the surface of a thin-core fiber modal interferometer (TCFMI) with a layer-by-layer (LbL) electrostatic self-assembly method. The fabricated TCFMI pH sensor has different transmission dip wavelengths under different pH values and shows high sensitivities of 0.6 nm/pH unit and −0.85 nm/pH unit for acidic and alkaline solutions, respectively, and short response time of 30–50 s. The LbL electrostatic self-assembly process of a PEC⁻/PDDA multilayer is traced by quartz crystal microbalance and shows a fast thickness growth. Atomic force microscopy shows the root mean square (RMS) surface roughness of electrostatic self-assembly nanocoating of polyelectrolyte complex/polyelectrolyte is much higher than that of polyelectrolyte/polyelectrolyte due to the larger size of PEC⁻ colloidal nanoparticles. The enhanced RMS surface roughness and thickness of the nanocoating can shorten the response time and raise the sensitivity of the TCFMI pH sensor, respectively. In addition, the TCFMI pH sensor has highly reversible performance and good durability.     

Cascade of coil-globule conformational transitions of single flexible polyelectrolyte molecules in poor solvent

We show that hydrophobic flexible polyelectrolyte molecules of poly(2-vinylpyridine) and poly(methacryloyloxyethyl dimethylbenzylammonium chloride) are trapped and frozen due to adsorption on the mica surface, and the observed AFM single molecule structures reflect the molecular conformation in solution. An increase of the ionic strength of the solution induces the cascade of abrupt conformational transitions due to the intrachain segregation from elongated coil to compact globule conformations through intermediate pearl necklace-globule conformations with different amounts of beads per chain. The length of the necklaces and the number of beads decrease, while the diameter of beads increases with the increase of ionic strength. Coexistence at the same time of extended coils, necklaces with different amounts of beads, and compact globules indicates the cascade of the first-order-type phase transitions.     

Covalent assembly of shortened multiwall carbon nanotubes on polyelectrolyte films and relevant electrochemistry study

A significant and versatile approach was developed for perpendicularly aligning multiwall carbon nanotubes on diverse substrates suitable for layer-by-layer self-assembly. The multiwall carbon nanotubes (s-MWNTs) used were shortened with oxidation under ultrasonic and functionalized with acyl chloride in thionyl chloride (SOCl2). The monolayer of s-MWNTs perpendicularly grafted to the substrate was obtained by dipping the polyelectrolyte modifying substrate into a tetrahydrofuran suspension of the functionalized s-MWNTs. The interaction proved to be stable and not liable to be affected by the ambience. Transmission electron microscopy and atomic force microscopy were used to examine the morphology of the MWNTs and s-MWNTs grafted on the substrates. Raman spectroscopy was applied to verify the existence of s-MWNTs for assembly, and Fourier transform infrared absorption spectra were used to investigate the interaction pattern between s-MWNTs and polyelectrolyte. The electrochemistry properties of the monolayer of s-MWNTs when the substrate was indium-tin oxide were studied.     

Transport diffusion of gases is rapid in flexible carbon nanotubes

Molecular dynamics simulations of rigid, defect-free single-walled carbon nanotubes have previously suggested that the transport diffusivity of gases adsorbed in these materials can be orders of magnitude higher than any other nanoporous material (A. I. Skoulidas et al., Phys. Rev. Lett. 2002, 89, 185901). These simulations must overestimate the molecular diffusion coefficients because they neglect energy exchange between the diffusing molecules and the nanotube. Recently, Jakobtorweihen et al. have reported careful simulations of molecular self-diffusion that allow nanotube flexibility (Phys. Rev. Lett. 2005, 95, 044501). We have used the efficient thermostat developed by Jakobtorweihen et al. to examine the influence of nanotube flexibility on the transport diffusion of CH4 in (20,0) and (15,0) nanotubes. The inclusion of nanotube flexibility reduces the transport diffusion relative to the rigid nanotube by roughly an order of magnitude close to zero pressure, but at pressures above about 1 bar the transport diffusivities for flexible and rigid nanotubes are very similar, differing by less than a factor or two on average. Hence, the transport diffusivities are still extremely large compared to other known materials when flexibility is taken into account.     

Highly controlled coating of biomimetic polydopamine in TiO2 nanotubes

Highly controlled coating of biomimetic polydopamine (PDA) was achieved on titanium dioxide nanotubes (TiO₂ NTs) by exposing TiO₂ NT arrays to a slightly alkaline dopamine solution. The thin films act as photonic sensitizers (enhancing photocurrents and photodegradation) in the visible light range. The PDA coatings can furthermore be used as a platform for decorating the TiO₂ NTs with different co-catalysts and metal nanoparticles (NPs).     

Structure of flexible and semiflexible polyelectrolyte chains in confined spaces of slit micro/nanochannels

Understanding the behavior of a polyelectrolyte in confined spaces has direct relevance in design and manipulation of microfluidic devices, as well as transport in living organisms. In this paper, a coarse-grained model of anionic semiflexible polyelectrolyte is applied, and its structure and dynamics are fully examined with Brownian dynamics (BD) simulations both in bulk solution and under confinement between two negatively charged parallel plates. The modeling is based on the nonlinear bead-spring discretization of a continuous chain with additional long-range electrostatic, Lennard-Jones, and hydrodynamic interactions between pairs of beads. The authors also consider the steric and electrostatic interactions between the bead and the confining wall. Relevant model parameters are determined from experimental rheology data on the anionic polysaccharide xanthan reported previously. For comparison, both flexible and semiflexible models are developed accompanying zero and finite intrinsic persistence lengths, respectively. The conformational changes of the polyelectrolyte chain induced by confinements and their dependence on the screening effect of the electrolyte solution are faithfully characterized with BD simulations. Depending on the intrinsic rigidity and the medium ionic strength, the polyelectrolyte can be classified as flexible, semiflexible, or rigid. Confined flexible and semiflexible chains exhibit a nonmonotonic variation in size, as measured by the radius of gyration and end-to-end distance, with changing slit width. For the semiflexible chain, this is coupled to the variations in long-range bond vector correlation. The rigid chain, realized at low ionic strength, does not have minima in size but exhibits a sigmoidal transition. The size of confined semiflexible and rigid polyelectrolytes can be well described by the wormlike chain model once the electrostatic effects are taken into account by the persistence length measured at long length scale.     

Amperometric choline biosensor fabricated through electrostatic assembly of bienzyme/polyelectrolyte hybrid layers on carbon nanotubes

We report a flow injection amperometric choline biosensor based on the electrostatic assembly of the choline oxidase (ChO) enzyme and a bienzyme of ChO and horseradish peroxidase (HRP) onto multi-wall carbon nanotubes (MWCNT) modified glassy carbon (GC) electrodes. These choline biosensors were fabricated by immobilization of enzymes on the negatively charged MWCNT surface through alternately assembling a cationic poly(diallydimethylammonium chloride) (PDDA) layer and an enzyme layer. Using this layer-by-layer assembling approach, a bioactive nanocomposite film of PDDA/ChO/PDDA/HRP/PDDA/CNT (ChO/HRP/CNT) and PDDA/ChO/PDDA/CNT (ChO/CNT) was fabricated on the GC surface. Owing to the electrocatalytic effect of carbon nanotubes, the measurement of faradic responses resulting from enzymatic reactions has been realized at low potential with acceptable sensitivity. The ChO/HRP/CNT biosensor is more sensitive than the ChO/CNT one. Experimental parameters affecting the sensitivity of biosensors, e.g., applied potential, flow rate, etc., were optimized and potential interference was examined. The response time for this choline biosensor is fast (few seconds). The linear range of detection for the choline biosensor is from 5.0 x 10(-5) to 5.0 x 10(-3) M and the detection limit is about 1.0 x 10(-5) M.     

稳定于碳纳米管的Pt高价态物种在不对称氢化反应中的作用

碳纳米管的独特性质,特别是其一维有序的管腔结构所形成的限域环境在催化反应中的应用引起了广泛的兴趣.已有将常规的液相氢化反应和气相反应限域于碳纳米管内的研究报道,并且大多数的研究结果显示限域于碳纳米管内的反应活性和/或选择性有明显提高,但多数研究没有对此给出清晰的解释.金鸡纳碱修饰的Pt催化剂催化的α-酮酸酯不对称氢化体系被认为是多相不对称催化领域发展的里程碑.早期的研究是简单的将碳纳米管作为Pt催化剂的载体用于α-酮酸酯不对称氢化反应,取得了中等的活性和对映体选择性.我们研究组发展了一种催化剂制备方法,可选择性的将Pt纳米粒子限域于碳纳米管管腔内或担载在碳纳米管管外,并将所制备的碳纳米管Pt催化剂应用于α-酮酸酯多相不对称催化反应中,发现封装于管腔内的管内型Pt纳米粒子的催化性能显著高于负载在管腔外壁的管外型Pt纳米粒子的催化性能.然而,对于管内型Pt催化剂催化性能增强的原因并不清楚. CO化学吸附和高分辨投射电镜(HRTEM)的表征结果表明管腔内外的Pt纳米粒子的大小和形貌没有明显区别.本论文在上述研究基础上,采用X射线光电子能谱(XPS),氢气程序升温脱附(H2-TPD),紫外可见光谱(UV-Vis)等表征手段研究了Pt纳米粒子担载于碳纳米管内和管外形成的催化剂在α-酮酸酯的不对称氢化反应中催化性能差异的原因. XPS测试结果表明,管内型和管外型Pt催化剂的载体的碳物种分布没有显出差异,但催化活性中心Pt纳米粒子的Pt物种组成不同.经225 oC H2还原后管外型Pt催化剂不存在高氧化态的Pt物种,而管内型Pt催化剂在400 oC H2还原仍然具有7%的高氧化态Pt物种.相应的催化反应结果表明,具有这种稳定的高氧化态Pt物种有利于获得高对映体选择性.参比催化剂商业化的Pt/AC和Pt/Al2O3的XPS测试结果也表明,对映体选择性高的Pt/Al2O3催化剂具有较高含量的高氧化态Pt物种.同时我们发现高氧化态Pt物种有利于催化剂对手性修饰剂和反应底物的吸附.虽然文献中一般认为Pt0是该反应的活性中心,但我们认为这些高氧化态的Pt物种有利于纳米粒子和手性修饰剂之间的相互作用,从而提高反应的对映选择性.我们进一步研究了表明高氧化态的Pt物种能存在于碳纳米管管腔内的原因.发现在催化剂制备过程中所使用的还原剂甲酸钠中残留的钠离子能稳定碳纳米管管腔内高氧化态Pt物种.我们采用H2直接还原制备了不含钠离子的参比管内型Pt催化剂.该参比催化剂的对映体选择性与管外型Pt催化剂相当,明显低于管内型Pt催化剂.同时该参比催化剂对手性修饰剂和底物的吸附能力弱于管内型Pt催化剂.以上结果清晰的表明了碳纳米管内由钠离子稳定的高氧化态Pt物种在α-酮酸酯多相不对称催化反应中的重要作用.然而,我们发现高氧化态Pt+物种含量的差异并不能很好的解释管内型和管外型Pt催化剂反应活性的差异. H2-TPD的结果表明相比于管外型Pt纳米粒子催化剂,管内型Pt纳米粒子具有更高的活化氢分子的能力,相应的催化反应结果表明,管外型Pt催化剂的反应活性随H2压力的降低而显著降低,而管内型Pt催化剂在0.1 MPa H2条件下仍然具有较高活性.简单的动力学模拟结果表明,在0.1 MPa H2条件下,碳纳米管管腔能显著富集H2.     

Alternate assemblies of polyelectrolyte functionalized carbon nanotubes and platinum nanoparticles as tunable electrocatalysts for dioxygen reduction

A novel method based on electrostatic layer-by-layer self-assembly (LBL) technique for alternate assemblies of polyelectrolyte functionalized multi-walled carbon nanotubes (MWNTs) and platinum nanoparticles (PtNPs) is proposed. The shortened MWNTs can be functionalized with positively charged poly(diallyldimethylammonium chloride) (PDDA) based on electrostatic interaction. Through electrostatic layer-by-layer assembly, the positively charged PDDA functionalized MWNTs (PDWNTs) and negatively charged citrate-stabilized PtNPs were alternately assembled on a 3-mercaptopropanesulfonic sodium (MPS) modified gold electrode and also on other negatively charged surface, e.g. quartz slide and indium–tin-oxide (ITO) plate, directly forming the three-dimensional (3D) nanostructured materials. This is a very general and powerful technique for the assembling three-dimensional nanostructured materials containing carbon nanotubes (CNTs) and nanoparticles. Thus prepared multilayer films were characterized by ultraviolet–visible–near-infrared spectroscopy (UV–vis–NIR), scanning electron microscopy (SEM) and cyclic voltammetry (CV). Regular growth of the mutilayer films is monitored by UV–vis–NIR. SEM provides the morphology of the multilayer films. The PtNPs containing multilayer films exhibit high electrocatalytic activity for the reduction of dioxygen. Furthermore, the electrocatalytic activity of the films could be further tailored by simply choosing different cycles in the LBL process. This assembling method for polyelectrolyte functionalized carbon nanotubes and nanoparticles introduces new opportunities for the incorporation of various functionalities into nanotube devices, which, in turn, opens up the possibility of building more complex multicomponent nanostructures.     

Rubber-based substrates modified with carbon nanotubes inks to build flexible electrochemical sensors

The development of a solid-contact potentiometric sensor based on conducting rubbers using a carbon nanotubes ink is described here. Commercial rubbers are turned into conductive ones by a simple and versatile method, i.e. painting an aqueous dispersion of single-walled carbon nanotubes on the polymer surface. On this substrate, both the working ion-selective electrode and the reference electrode are built in order to form an integrated potentiometric cell. As a proof-of-principle, selective potassium electrodes are fully characterized giving comparable performances to conventional electrodes (sensitivity, selectivity, stability, linear range, limit of detection and reproducibility). As an application of the rubber-based electrodes, a bracelet was constructed to measure potassium levels in artificial sweat. Since rubbers are ubiquitous in our quotidian life, this approach offers great promise for the generation of chemical information through daily objects.     

Mean field theory for the intermolecular and intramolecular conformational transitions of a single flexible polyelectrolyte chain

The diMarzio theory has been extended to elucidate the intermolecular and intramolecular phase segregations of a single flexible chain polyelectrolyte in dilute salt-free solutions. At the long chain limit, this theory yields the formalism obtained from the more sophisticated Edward Hamiltonian for polyelectrolyte problems. The calculated phase diagram exhibits the features of a first-order phase transition, with continuous and discontinuous transitions separated by a critical point. Under the discontinuous transition, the polyelectrolyte chain exhibits coexistent expanded and collapsed conformational states, same as intermolecular phase segregation. For a limiting long chain, the mean chain size at critical point is roughly 90% of the size of an ideal chain. Such a result implies that partial contraction within a chain molecule is required to collapse a flexible polyelectrolyte chain. Moreover, the theory predicts that for a longer chain, intramolecular segregated conformations differ significantly from intermolecular segregated conformations, but the difference becomes small for shorter chains. Besides, the charge needed to induce intramolecular segregation is smaller than that of intermolecular segregation for a given chain length. These findings are consistent with previous literature results.     

Threading-unthreading equilibrium in solution of molecular nanotubes and linear flexible polymer chains

Using the Flory-Huggins lattice model, we investigate the threading-unthreading equilibrium in a solution of linear flexible polymer chains and molecular nanotubes formed by covalently bonding the ringlike molecules, such as cyclodextrins (CDs). It is found that the threading-unthreading equilibrium depends on the temperature and the molar concentrations of the ringlike molecules and polymer chain segments but is independent of the polymer chain length, which agrees with the experimental observations. By fitting the experimental data of alpha-CD and poly(ethylene glycol) (PEG), the inclusion energy between alpha-CD and PEG, which includes the conformation energy loss of PEG resulted from the inclusion, is calculated to be approximately -20.45 kJ/mol per PEG unit.     

Highly dispersed sulfur in multi-walled carbon nanotubes for lithium/sulfur battery

A facile method is developed for homogeneous dispersion of sulfur (S) nanoparticles in multi-walled carbon nanotubes (MWCNTs). The process involves the modification of MWCNTs via oxidation catalyzed by acid and the introduction of sulfur nanoparticles into the MWCNTs through direct precipitation. The resulting sample (precipitated S/MWCNTs) is characterized with scanning electron microscopy and thermogravimetric analysis, and its performance as cathode of lithium/sulfur battery is investigated with a comparison of the sample prepared by ball-milling (ball-milling S/MWCNTs). It is found that the precipitated S/MWCNTs exhibit better battery performance than the ball-milling S/MWCNTs. The initial discharge capacity is 1,299 mA?h?g^?1 for the precipitated S/MWCNTs but only 839 mA?h?g^?1 for ball-milling S/MWCNTs at 0.02 C. The capacity remains 800 mA?h?g^?1 for the precipitated S/MWCNTs but only 620 mA?h?g^?1 for ball-milling S/MWCNTs at 0.05 C after 50 cycles. The better performance of the precipitated S/MWCNTs results from the improved uniformity of S dispersed in MWCNTs through precipitation.