Formation and morphological characteristics of selenium-containing nanostructures based on rigid-chain cellulose derivatives

Nanostructures arising from the reduction of ionic selenium by a selenite-ascorbate redox system in aqueous solutions of oxyethyl cellulose, methyl cellulose, and carboxymethyl cellulose have been studied by using a set of optical methods (flow birefringence and static and dynamic light scattering) and viscometry. The adsorption of a substantial amount of macromolecules (up to 3200) on selenium nanoparticles has been experimentally discovered. This effect leads to the formation of superhigh-molecular-mass spherical nanostructures with a high density of the polymer shell. The thermodynamic state of solutions of nanostructures has been characterized. In the region of occurrence of stable dispersions, the values of the free energy of macromolecule-selenium nanoparticle interaction have been calculated for polymer nanostructures. Radii of amorphous selenium nanoparticles occurring in the nuclei of nanostructures and the thickness of the polymer shell have been estimated. Given the fixed molecular mass and comparable rigidity of a polymer matrix, the structure of the monomer unit of the cellulose derivative defines the morphology of the nanostructure being formed.     

Morphological characteristics of selenium-containing nanostructures based on rigid-chain molecules

Selenium-containing nanostructures of rigid-chain polymers with close molecular masses were studied by flow birefringence (FB) and static and dynamic light scattering at a fixed selenium to polymer mass ratio ν = 0.1 in solution. The group of polymers under study included the cationic polyelectrolyte poly-N,N,N,N-trimethylmethacryloyloxyethylammonium methyl sulfate, anionic polyelectrolyte carboxymethylcellulose, and nonionogen polymer oxyethylcellulose. High-molecular selenium-containing polymer nanostructures were found in all cases. Nanostructures with a maximum molecular mass and the largest number of constituent macromolecules were obtained using oxyethylcellulose. At ν = 0.1 the mean square radii of inertia of the nanostructures were almost independent of the nature of the polymer matrix. The thermodynamic state of the solutions of nanostructures was close to the ideal one in all cases. For the region where stable dispersions formed, the Gibbs energies of macromolecule-selenium nanoparticle interactions were calculated and shown to be almost independent of the nature of the polymer matrix at ν = 0.1. The close mean square radii of inertia R _g^* of the nanostructures, the Gibbs energies of interaction, and the equivalence of the thermodynamic state of the solutions of nanostructures obtained for all polymer matrices at ν = 0.1 suggest that ν = 0.1 corresponds to the ultimate adsorption capacity of selenium nanoparticles; the considerable differences between the molecular masses (for close R _g ^* values), mean densities, and structural conformation parameters ρ* point to different packings of macromolecules in the nanostructures under study.     

The Influence of Polymer—Selenium Complex Components and the Molecular Weight of the Ionogenic Polymeric Matrix on the Morphologic Characteristics of Selenium-Containing Nanostructures

Several optical methods were used to study nanostructures formed in the reduction of selenium ions in the selenite—ascorbate redox system in an aqueous solution of the poly-N,N,N,N-trimethylmethacryloyloxyethylammonium methyl sulfate polycation. The relation between the molecular weight of the polymeric matrix, which varied over a wide range, M _w = (0.03?13) × 10⁶, and the morphologic characteristics of nanostructures (molecular weight, density, shape, and statistical and hydrodynamic dimensions) was established. The weight ratio between the components of the polymer: selenium complex and the concentration of the polymer in the reaction mixture were shown to substantially influence certain morphologic characteristics of nanostructures. In the region of the formation of stable dispersions, the Gibbs energy of macromolecule—Se⁰ nanoparticle interactions was calculated. The thermodynamic state of solutions of nanostructures was characterized.     

Structural-morphological and biological properties of selenium nanoparticles stabilized by bovine serum albumin

Nanostructures formed during the reduction of ionic selenium in the selenite-ascorbate redox system in an aqueous solution of bovine serum albumin (BSA) were studied using static and dynamic light scattering and flow birefringence. It was established that this process results in the formation of stable aggregates of selenium nanoparticles that adsorb BSA molecules. It was found that highly-ordered superhigh-molecular-weight spherical nanostructures with high density and unique morphology are formed. Experiments with a cell culture of promyelocytic leukemia HL-60 showed that BSA adsorbed on selenium nanoparticles can inhibit the growth of tumor cells and deactivate free radicals with an efficiency comparable with that of sodium selenite.     

Ionic Conductivity in Solutions of Poly(ethylene oxide) and Lithium Perchlorate

Summary: Solution casting technique served to prepare solid solutions of lithium perchlorate and poly(ethylene oxide) (PEO) having different molecular masses. Salt concentrations of solutions were varied between around 2 and 13 wt%. Crystallinity and melting point depression served to determine composition and content of amorphous phase as well as thermodynamic behavior of the solutions. Conductivity as a function of salt concentration in the amorphous phase follows a power law at constant temperature (30 °C). It results that both exponent and mobility of charge carriers increase with ascending molecular mass of PEO. The mobility follows an increase with molecular mass proportional to M^2.8 indicating dependence of mobility on interstitial volume between chain molecules. Deviation of solution from perfect behavior can be evaluated by melting point depression. Accordingly, increase in conductivity is preferably related to approach to perfect solution behavior. Determination of dielectric function allows some conclusion about ion pair formation in the systems under discussion. It turns out that probability of ion pair formation decreases with increasing molecular mass of PEO in agreement with thermodynamic behavior of the solutions.     

Self-organization and morphological characteristics of selenium-containing nanostructures based on rigid-chain polymers

Macroinitiators containing β-diketonate fragments were prepared by copolymerization of styrene with cobalt(II) 5-Formation and morphological characteristics of selenium-containing nanostructures formed by reduction of selenious acid with ascorbic acid in the presence of ionic or nonionic polymeric stabilizer in aqueous solutions were studied by methods of nonlinear optics and flow birefringence at widely varied selenium to polymer weight ratio in solution ν. The molecular weights, root-mean-square and hydrodynamic sizes, and mean density of the nanostructures were calculated, and the trends in variation of these quantities were compared.     

The influence of the ratio between the selenium: Polyvinylpyrrolidone complex components on the formation and morphological characteristics of nanostructures

Optical and spectral methods were used to study nanostructures formed in the reduction of ionic selenium in the selenite-ascorbate redox system in aqueous solutions of polyvinylpyrrolidone, a physiologically active polymer. The weight ratio between the selenium: polymer complex components (ν) was varied over a wide range (ν = 0.01?0.2). The adsorption of a substantial number of macromolecules (up to 1000 at ν = 0.1?0.2) on selenium nanoparticles was observed experimentally. This resulted in the formation of supramolecular spherical nanostructures with a high polymeric shell density. The Gibbs energies of macromolecule-Se⁰ nanoparticle interactions were calculated for polymeric nanostructures in the region of the formation of stable dispersions. The flow birefringence, dynamic light scattering, and spectrophotometry methods were used to determine the region of saturation of the adsorption capacity of selenium nanoparticles in selenium-containing nanocomposites (ν = 0.1?0.2).     

聚乙烯吡咯烷酮辅助的水热法合成形貌可控的银纳米结构

以不同平均分子质量的聚乙烯吡咯烷酮(PVP,通常用K值来表示PVP溶液相对粘度的特征值,粘度越大,PVP平均分子质量越大,平均分子质量为8000、40000、160000、360000的PVP分别标记为K17、K30、K60、K90)为表面活性剂,通过水热法合成了形貌和光学共振峰可控的银纳米结构.将反应体系加入到60 mL的不锈钢高压反应釜中,在一定的温度下加热数小时.我们在K17的水溶液中合成了尺寸均一的五重孪晶银纳米十面体.而在K30、K60和K90的乙二醇(EG)溶液中得到了纵横比随着PVP分子质量增大而增大的银纳米线.产物的形貌和微结构通过透射电镜(TEM)和场发射扫描电镜(FE-SEM)进行表征,表面等离子共振(SPR)吸收峰通过紫外-可见分光光度计进行测试,结果显示银纳米结构的表面等离子共振随着其形貌和尺寸的改变而发生变化.     

Solution-phase synthesis and electrochemical hydrogen storage of ultra-long single-crystal selenium submicrotubes

Ultra-long single-crystalline trigonal selenium submicrotubes were synthesized using a facile one-step solution-phase approach with the assistance of nonionic surfactant Polyoxyethylene(20)sorbitan monolaurate (Tween-20), which turned out to be significant for the formation of ultra-long Se submicrotubes. XRD, Raman, SEM, and TEM were adopted to characterize the morphology, structure and phase composition of the as-prepared Se products. It was found that the length of the obtained Se submicrotubes was over 100 microm. By variation of the experimental parameters, the t-Se spheres, nanowires, and broken microtubes can be prepared. The possible growth mechanism of the ultra-long selenium submicrotubes was explained. In addition, we have also demonstrated that the synthesized ultra-long t-Se submicrotubes using the Tween-20-assisted approach can electrochemically charge and discharge with the high capacity of 265 mAh/g (corresponding to 0.97 wt % hydrogen in SWNTs) under normal atmosphere at room temperature. Cyclic voltammetry was adopted to investigate the adsorption-oxidation behavior of ultra-long selenium submicrotubes. It was observed that the morphology of the synthesized selenium products had a remarkable influence on their capacity of electrochemical hydrogen storage. These differences in hydrogen storage capacity are likely due to the size and density of tubes as well as the microcosmic morphology of different Se samples. The as-obtained ultra-long Se submicrotubes are expected to find wide applications in hydrogen storage, high-energy batteries, and optoelectronic, biologic, and catalytic fields as well as in the studies of structure-property relationships. This simple Tween-assisted approach might be extended to the preparations of one-dimensional nanostructures of tellurium and other anisotropic materials.     

表面活性剂控制的硒纳米线的室温生长

以表面活性剂十二烷基硫酸钠(SDS)为形貌导向剂,利用Na₂Se在室温碱性水溶液中的自发氧化,成功制备了Se纳米线。用TEM、SEM、EDX、XRD、HRTEM、SEAD等手段表征了Se纳米线的组成和结构。结果表明,合成的Se纳米线是沿六方相Se的[001]轴方向生长,具有良好的晶型结构。使用TEM对不同时间Se纳米结构的生长过程的形貌进行了跟踪,探讨了Se纳米线的形成机理,发现其形成与生长过程符合“solid-solution-solid”机理。同时,选择了具有特异官能团(如-OH,-COOH,-CONH₂)的3种表面活性剂,研究它们在纳米硒的取向性生长中的导向作用,只有SDS能引导合成出高质量的Se纳米线。     

The influence of the nature of a nanoparticle and polymer matrix on the morphological characteristics of polymeric nanostructures

Comparative studies of the morphological characteristics of selenium- and platinum-containing nanostructures were performed by molecular optics methods. The nanostructures were based on an ionogenic polymeric stabilizer, poly-N,N,N,N-trimethylmethacryloyloxyethylammonium methyl sulfate, and a non-ionogenic polymeric stabilizer, oxyethylcellulose. Studies were performed in aqueous solutions at a fixed ratio between components. The adsorption of a considerable number of polymer macromolecules on nanoparticles with the formation of superhigh-molecular-weight nanostructures with shapes close to spherical was observed for all the nanosystems studied. The thermodynamic state of nanosystems was characterized. Certain morphological characteristics of nanostructures were substantially influenced by the nature of both nanoparticles and polymer matrix.     

Speciation of selenium in selenium-enriched shiitake mushroom, Lentinula edodes

The major selenium compound in an aqueous extract of the most popular mushroom in Eastern Asian countries, shiitake (Lentinula edodes), fortified with selenium (Se) was identified by means of hyphenated techniques, i.e. HPLC-inductively coupled argon plasma mass spectrometry and HPLC-electrospray ionization mass spectrometry (HPLC–ICP MS and HPLC–ESI MS). Sixty-eight per cent of the total Se in the selenized shiitake was extracted with water, and 49.8% of the Se in the water extract was eluted in the high molecular mass fraction (>40,000 kDa) before incubation at 37 °C. After incubation, 40.6% of the Se in the water extract was eluted in a lower molecular mass fraction and the Se eluted in the high molecular mass fraction had decreased to 14.0%, suggesting that the major selenium compound in the water extract was initially in a form bound to macromolecule(s) and was then enzymatically liberated from the macromolecule(s). The retention time of the liberated selenium compound in HPLC–ICP MS matched that of selenomethionine (SeMet), and the masses of molecular and fragment ions detected by HPLC–ESI MS also suggested that the selenium compound was SeMet. The selenized shiitake accumulated Se as SeMet, and SeMet might be bound to the water extractable high molecular mass protein(s).Electronic Supplementary Material Supplementary material is available for this article at     

Iridium Modifier for Determination of Selenium by Graphite Furnace Atomic Absorption Spectrometry

ABSTRACT

The behaviour of thermally reduced or electrodeposited iridium modifier in graphite furnace atomic absorption spectrometry (GFAAS) for the determination of selenium was investigated. The performance of modification for standard solution of selenium as well as in the presence of chloride containing matrix (e.g. sea water) was examined. It was found that the graphite material plays a significant role in the determination of volatile elements by the formation of graphite intercalation compounds. Those compounds are responsible for the long-term performance of stabilisation of selenium in chloride containing solutions.     

Aggregation work at polydisperse micellization: ideal solution and "dressed micelle" models comparing to molecular dynamics simulations

General thermodynamic relations for the work of polydisperse micelle formation in the model of ideal solution of molecular aggregates in nonionic surfactant solution and the model of "dressed micelles" in ionic solution have been considered. In particular, the dependence of the aggregation work on the total concentration of nonionic surfactant has been analyzed. The analogous dependence for the work of formation of ionic aggregates has been examined with regard to existence of two variables of a state of an ionic aggregate, the aggregation numbers of surface active ions and counterions. To verify the thermodynamic models, the molecular dynamics simulations of micellization in nonionic and ionic surfactant solutions at two total surfactant concentrations have been performed. It was shown that for nonionic surfactants, even at relatively high total surfactant concentrations, the shape and behavior of the work of polydisperse micelle formation found within the model of the ideal solution at different total surfactant concentrations agrees fairly well with the numerical experiment. For ionic surfactant solutions, the numerical results indicate a strong screening of ionic aggregates by the bound counterions. This fact as well as independence of the coefficient in the law of mass action for ionic aggregates on total surfactant concentration and predictable behavior of the "waterfall" lines of surfaces of the aggregation work upholds the model of "dressed" ionic aggregates.     

Effects of metal–ligand coordination on the self-assembly behaviour of a crown ether functionalised perylenetetracarboxylic diimide

A novel perylenetetracarboxylic diimide (PDI) derivative, N,N′-di(4′-benzo-15-crown-5-ether)-1,7-di(4-tert-butyl-phenoxy)perylene-3,4;9,10-tetracarboxylic diimide (CRPDI), has been synthesised and characterised. Dimerisation of CRPDI is induced by the presence of K⁺ in CHCl₃ or spontaneously occurs in methanol, as revealed by absorption and emission spectroscopy. In particular, the formation of co-facial dimer in the presence of K⁺ proceeds in a three-stage process, as indicated by absorption spectroscopy. The belt- and rope-like nanostructures of CRPDI fabricated from methanol and CHCl₃ solution in the presence of K⁺ are obtained by scanning electron microscopy. Furthermore, the conductivity of the rope-like nanostructures from the cation-induced dimeric species is more than ca. 1 order of magnitude higher than the belt-like nanostructures from the solvent-induced dimeric species. The present result represents the further effort towards realisation of controlling and tuning the morphology of self-assembled nanostructures of PDI derivatives through molecular design and synthesis. It will be valuable for the design and preparation of PDI-based nano-(opto)electronic devices with good performance due to the close relationship between the molecular ordering and dimensions of nanostructures and the performance of nanodevices.     

Fabrication of virus-like particles with strip-pattern surface: A two-step self-assembly approach

Spherical nanostructures with striped patterns on the surfaces resembling the essential structures of natural virus particles were constructed through a two-step self-assembly approach of polystyrene-boligo(acrylic acid)(PS-b-oligo-AA) and poly(γ-benzyI L-glutamate)-b-poly(ethylene glycol)(PBLG-bPEG) copolymer mixtures in solution.On the basis of difference in hydrophilicity and self-assembly properties of the two copolymers,the two-step self-assembly process is realized.It was found that PS-boligo-AA copolymers formed spherical aggregates by adding a certain amount of water into polymer solutions in the first step.In the second step,two polymer solutions were mixed and water was further added,inducing the self-assembly of PBLG-b-PEG on the surfaces of PS-b-oligo-AA spheres to form striped patterns.In-depth study was conducted for the indispensable defects of striped patterns which are dislocations and +1/2 disclinations.The influencing factors such as the mixing ratio of two copolymers and the added water content in the first step on the morphology and defects of the striped patterns were investigated.This work not only presents an idea to interpret mechanism of the cooperative self-assembly behavior,but also provides an effective approach to construct virus-like particles and other complex structures with controllable morphology.     

Controlled self-assembly of triphenylene-based molecular nanostructures

Molecular nanostructures of the disc-shaped molecule hexapentyloxytriphenylene have been fabricated on length scales ranging from 30 nm to 1.5 mum following self-assembly arising from pi-pi interactions in organic solvents. The size and density of the molecular nanostructures deposited onto glass and indium tin oxide-coated glass substrates were characterized by atomic force microscopy. Dynamic light scattering and spectroscopic evidence of predeposition aggregation in solution are presented, suggesting that the nanostructures are organized in solution and then deposited onto the substrate. Correlations between the relative solvent polarity and the size of molecular nanostructures as well as between the solute concentration in dilute solutions and their density on the substrate are discussed.     

两性聚电解质溶液的分子热力学模型和分子动力学模拟

从带电硬球混合物出发采用化学缔合理论建立了聚电解质和两性聚电解质溶液的分子热力学模型.用考虑溶剂的粘滞力和热浴随机力作用的分子动力学(MD)方法模拟了聚电解质和两性聚电解质溶液的渗透系数.对模型预测结果和MD模拟结果进行了比较,表明基于化学缔合理论的分子热力学模型可以用于聚电解质溶液和两性聚电解质溶液热力学性质的预测,对于均聚电解质溶液效果令人满意,对由直径不同的离子构成的聚电解质溶液,模型的预测效果变差,有待进一步改进.该模型对两性聚电解质溶液渗透系数的预测效果比对聚电解质溶液的预测效果更好.     

The polymeric nature of selenium crystallization. I. Morphology and thermodynamic considerations

The morphology of selenium has been studied in light of present concepts of crystallinity in crystalline organic polymers. Spherulitic crystallization and resultant morphology were examined as a function of temperature by transmission and replication electron microscopy, electron diffraction, and optical microscopy. Evidence is given for polymer chain folding during crystallization of trigonal selenium. Theoretical thermodynamic calculations presented yield several thermodynamic values including an equilibrium melting point of 219.2°C, a fold surface energy of 337 ergs/cm² and a lateral surface energy of 9.8 ergs/cm².     

Thermal Properties and Morphology of Poly(Ester-Urethanes) Prepared from Polycaprolactone-Diol

The soft segment crystallinity and morphology of poly(ester-urethanes) (PEUs) based on poly(ε-caprolactone) (PCL) as a soft segment and an aliphatic diisocyanate in the hard segment were studied. It was found that the restriction of the crystallization of the PCL soft segment depends on the hard segment concentration, the length of the soft segment, and the total molecular mass of the PEUs. The PEU based on a low molecular mass PCL (M=2000) is an amorphous elastic material during a long time after casting from solution or after melt crystallization. A soft-hard segment endothermal mixing transition (T_mix) of about 70-80°C is observed in the DSC curves of this PEU sample. This revised version was published online in August 2006 with corrections to the Cover Date.