Binuclear ion containing nitrogen as a bridging group

A binuclear ion ([NH(3))5RuN(2)Ru(NH(3))(5)](5)+ is formed by the direct reaction of N(2) with an aqueous solution of (NH(3))(5)RuOH(2)(2+) at room temperature. The binuclear ion is also formed by the reversible reaction of (NH(3))5RuOH(2)(2+) with (NH(3))(5)RuN(2)(2+). Solid [(NH(3))(5)RuN(2)Ru(NH(3))(5)] (BF(4))(4) has been prepared, and its ultraviolet and infrared spectra are reported.     

Synthesis of large arrays of well-aligned carbon nanotubes on glass

Free-standing aligned carbon nanotubes have previously been grown above 700 degreesC on mesoporous silica embedded with iron nanoparticles. Here, carbon nanotubes aligned over areas up to several square centimeters were grown on nickel-coated glass below 666 degreesC by plasma-enhanced hot filament chemical vapor deposition. Acetylene gas was used as the carbon source and ammonia gas was used as a catalyst and dilution gas. Nanotubes with controllable diameters from 20 to 400 nanometers and lengths from 0. 1 to 50 micrometers were obtained. Using this method, large panels of aligned carbon nanotubes can be made under conditions that are suitable for device fabrication.     

Direct synthesis of long single-walled carbon nanotube strands

In the processes that are used to produce single-walled nanotubes (electric arc, laser ablation, and chemical vapor deposition), the typical lengths of tangled nanotube bundles reach several tens of micrometers. We report that long nanotube strands, up to several centimeters in length, consisting of aligned single-walled nanotubes can be synthesized by the catalytic pyrolysis of n-hexane with an enhanced vertical floating technique. The long strands of nanotubes assemble continuously from arrays of nanotubes, which are intrinsically long.     

A discrete self-assembled metal array in artificial DNA

DNA has a structural basis to array functionalized building blocks. Here we report the synthesis of a series of artificial oligonucleotides, d(5'-GH(n)C-3') (n = 1 to 5), with hydroxypyridone nucleobases (H) as flat bidentate ligands. Right-handed double helices of the oligonucleotides, nCu2+.d(5'-GH(n)C-3')2 (n = 1 to 5), were quantitatively formed through copper ion (Cu2+)-mediated alternative base pairing (H-Cu2+-H), where the Cu2+ ions incorporated into each complex were aligned along the helix axes inside the duplexes with the Cu2+-Cu2+ distance of 3.7 +/- 0.1 angstroms. The Cu2+ ions were coupled ferromagnetically with one another through unpaired d electrons to form magnetic chains.     

Direct electrochemical measurements inside a 2000 angstrom thick polymer film by scanning electrochemical microscopy

An extremely small, conically shaped Pt microelectrode tip (with a radius of 30 nanometers) and the precise positioning capabilities of the scanning electrochemical microscope were used to penetrate a thin (200 nanometers) polymer film and obtain directly the standard potential and kinetic parameters of an electrode reaction within the film. The thickness of the film was determined while it was immersed in and swollen by an electrolyte solution. The film studied was the perfluorosulfonate Nafion containing Os(bpy)(3)(2+) (bpy, 2,2'-bipyridine) cast on an indium tin oxide surface. The steady-state response at the ultramicroelectrode allowed direct determination of the rate constant for heterogeneous electron transfer K(o) and the diffusion coefficient D without complications caused by transport in the liquid phase, charge exchange at the liquid-polymer interface, and resistive drop.     

Chemically derived, ultrasmooth graphene nanoribbon semiconductors

We developed a chemical route to produce graphene nanoribbons (GNR) with width below 10 nanometers, as well as single ribbons with varying widths along their lengths or containing lattice-defined graphene junctions for potential molecular electronics. The GNRs were solution-phase-derived, stably suspended in solvents with noncovalent polymer functionalization, and exhibited ultrasmooth edges with possibly well-defined zigzag or armchair-edge structures. Electrical transport experiments showed that, unlike single-walled carbon nanotubes, all of the sub-10-nanometer GNRs produced were semiconductors and afforded graphene field effect transistors with on-off ratios of about 10(7) at room temperature.     

Macroscopic, neat, single-walled carbon nanotube fibers

Well-aligned macroscopic fibers composed solely of single-walled carbon nanotubes (SWNTs) were produced by conventional spinning. Fuming sulfuric acid charges SWNTs and promotes their ordering into an aligned phase of individual mobile SWNTs surrounded by acid anions. This ordered dispersion was extruded via solution spinning into continuous lengths of macroscopic neat SWNT fibers. Such fibers possess interesting structural composition and physical properties.     

Aligned carbon nanotube films: production and optical and electronic properties

Carbon nanotube material can now be produced in macroscopic quantities. However, the raw material has a disordered structure, which restricts investigations of both the properties and applications of the nanotubes. A method has been developed to produce thin films of aligned carbon nanotubes. The tubes can be aligned either parallel or perpendicular to the surface, as verified by scanning electron microscopy. The parallel aligned surfaces are birefringent, reflecting differences in the dielectric function along and normal to the tubes. The electrical resistivities are anisotropic as well, being smaller along the tubes than perpendicular to them, because of corresponding differences in the electronic transport properties.     

Electron-tunneling pathways in cytochrome C

Distant Fe(2+)-Ru(3+) electronic couplings have been extracted from intramolecular electrontransfer rates in Ru(histidine(x)) (where X = 33, 39, 62, and 72) derivatives of cytochrome c. The couplings increase according to 62 (0.0060) < 72 (0.057) < 33 (0.097) < 39 (0.11 per wave numbers); however, this order is out of line with the histidine to heme edge-edge distances [62 (14.8) > 39 (12.3) > 33 (11.1) > 72 (8.4 angstroms)]. The rates (and the couplings) correlate with the lengths of sigma-tunneling pathways comprised of covalent bonds, hydrogen bonds, and through-space jumps from the histidines to the heme group. Space jumps greatly decrease couplings: One from Pro(71) to Met(80) extends the sigma-tunneling length of the His(72) pathway by roughly 10 covalent-bond units.     

改性填料强化组合MBR处理印染废水的效果研究

以改性填料作为填料组成的膜生物反应器处理某印染废水,考察了系统对污染物去除效果及减缓膜污染方面的作用。结果表明,反应器对COD和NH3-N均有着较高的去除效果,当进出水COD浓度分别为436～1 722 mg/L、43～79 mg/L,进出水NH3-N浓度分别为160～245 mg/L、6.6～16.8 mg/L时,COD、NH3-N的去除率分别为88.99%～96.93%9、0.69%～95.94%。其出水水质达到《城镇污水处理厂污染物排放标准》(GB18918-2002)二级标准。抽吸时间20 min时的膜过滤阻力上升较快,而抽吸时间15 min能较好地维持膜通量,保持膜过滤性能的稳定。在膜通量为11.2 L/(m2.h)情况下,透膜压差随运行时间的递增而呈现缓慢上升的趋势,改性填料对减轻膜污染的贡献明显;ρ(MLVSS)/ρ(MLSS)比值与SOUR的变化趋势基本保持一致,该系统内生物膜含有较高的挥发性有机成分,具有较高的活性。改性填料的投加有效地减轻了膜污染,大大延长了膜清洗的工作周期。     

环吡酮胺涂膜剂控释机理研究

研究了环吡酮胺涂膜剂,探讨涂膜的控释机理。方法利用双室渗透扩散装置进行离体皮肤体外渗透试验,通过改变聚合物膜的厚度研究其释药机理。结果涂膜剂中环吡酮胺以零级动力学透过皮肤,渗透速率与聚合物限速膜厚度的倒数呈良好性关系。结论环吡酮胺涂膜剂具有膜控型释药机理。     

PVC-壳聚糖絮凝作用延缓膜污染的效果

以PAC-壳聚糖为絮凝剂,通过絮凝试验考察了壳聚糖投加浓度分别为1,3,5,7,10mg·L-1及PAC为5mg·L-1时,对膜生物反应器中污泥混合液性能的影响。试验结果表明,壳聚糖能明显降低污泥混合液SUV254及SMP的浓度;对污泥混合液的粘度和污泥脱氢酶活性的影响也较小;壳聚糖投加量7mg·L-1的MBR处理人工废水的试验结果表明,添加PAC-壳聚糖的MBR的跨膜压力增大的同时,处理系统的膜通量也保持稳定,膜通量衰减速度及出水浊度等参数均低于对照组,说明PAC-壳聚糖絮凝作用对延缓膜污染有积极作用。     

Unexpected square symmetry seen by atomic force microscopy in bilayer films of disk-like molecules

Thin films of disk-shaped molecules are expected to display anisotropic optical and transport properties, leading to applications in optical display or sensor technologies. Bilayer Langmuir-Blodgett films of monomeric triphenylene mesogens have been studied by atomic force microscopy. The triphenylene cores of the constituent molecules tend to promote the formation of columnar structures in the plane of the substrate and along the direction of deposition of the film. Atomic force microscopy images of bilayer Langmuir-Blodgett films revealed two types of structure, one corresponding to an aligned columnar structure and the other to an unusual square lattice, which may result from the superposition of columnar structures in adjacent layers that intersect at near right angles. Annealing such bilayers near the melting point of the bulk compound improved the structural ordering by reducing the angular spread of orientations associated with the well-developed columnar structure in some areas and by producing a more distinct square lattice in other areas of the sample.     

Engineering carbon nanotubes and nanotube circuits using electrical breakdown

Carbon nanotubes display either metallic or semiconducting properties. Both large, multiwalled nanotubes (MWNTs), with many concentric carbon shells, and bundles or "ropes" of aligned single-walled nanotubes (SWNTs), are complex composite conductors that incorporate many weakly coupled nanotubes that each have a different electronic structure. Here we demonstrate a simple and reliable method for selectively removing single carbon shells from MWNTs and SWNT ropes to tailor the properties of these composite nanotubes. We can remove shells of MWNTs stepwise and individually characterize the different shells. By choosing among the shells, we can convert a MWNT into either a metallic or a semiconducting conductor, as well as directly address the issue of multiple-shell transport. With SWNT ropes, similar selectivity allows us to generate entire arrays of nanoscale field-effect transistors based solely on the fraction of semiconducting SWNTs.     

Fast mass transport through sub-2-nanometer carbon nanotubes

We report gas and water flow measurements through microfabricated membranes in which aligned carbon nanotubes with diameters of less than 2 nanometers serve as pores. The measured gas flow exceeds predictions of the Knudsen diffusion model by more than an order of magnitude. The measured water flow exceeds values calculated from continuum hydrodynamics models by more than three orders of magnitude and is comparable to flow rates extrapolated from molecular dynamics simulations. The gas and water permeabilities of these nanotube-based membranes are several orders of magnitude higher than those of commercial polycarbonate membranes, despite having pore sizes an order of magnitude smaller. These membranes enable fundamental studies of mass transport in confined environments, as well as more energy-efficient nanoscale filtration.     

Three-dimensionally ordered array of air bubbles in a polymer film

We report the formation of a three-dimensionally ordered array of air bubbles of monodisperse pore size in a polymer film through a templating mechanism based on thermocapillary convection. Dilute solutions of a simple, coil-like polymer in a volatile solvent are cast on a glass slide in the presence of moist air flowing across the surface. Evaporative cooling and the generation of an ordered array of breath figures leads to the formation of multilayers of hexagonally packed water droplets that are preserved in the final, solid polymer film as spherical air bubbles. The dimensions of these bubbles can be controlled simply by changing the velocity of the airflow across the surface. When these three-dimensionally ordered macroporous materials have pore dimensions comparable to the wavelength of visible light, they are of interest as photonic band gaps and optical stop-bands.     

Large-Scale Synthesis of Aligned Carbon Nanotubes

Large-scale synthesis of aligned carbon nanotubes was achieved by using a method based on chemical vapor deposition catalyzed by iron nanoparticles embedded in mesoporous silica. Scanning electron microscope images show that the nanotubes are approximately perpendicular to the surface of the silica and form an aligned array of isolated tubes with spacings between the tubes of about 100 nanometers. The tubes are up to about 50 micrometers long and well graphitized. The growth direction of the nanotubes may be controlled by the pores from which the nanotubes grow.     

Conducting Layered Organic-inorganic Halides Containing <110>-Oriented Perovskite Sheets

Single crystals of the layered organic-inorganic perovskites, [NH(2)C(I=NH(2)](2)(CH(3)NH(3))m SnmI3m+2, were prepared by an aqueous solution growth technique. In contrast to the recently discovered family, (C(4)H(9)NH(3))(2)(CH(3)NH(3))n-1SnnI3n+1, which consists of (100)-terminated perovskite layers, structure determination reveals an unusual structural class with sets of m <110>-oriented CH(3)NH(3)SnI(3) perovskite sheets separated by iodoformamidinium cations. Whereas the m = 2 compound is semiconducting with a band gap of 0.33 +/- 0.05 electron volt, increasing m leads to more metallic character. The ability to control perovskite sheet orientation through the choice of organic cation demonstrates the flexibility provided by organic-inorganic perovskites and adds an important handle for tailoring and understanding lower dimensional transport in layered perovskites.     

碳纳米管改性的蜡基复合粘结剂

通过熔融共混将功能化的碳纳米管引入到蜡基粘结剂中,得到碳纳米管改性的复合粘结剂.扫描电镜（SEM）显微照片显示,功能化的碳纳米管能均匀分散在粘结剂基体中.偏光显微照片和热性能分析结果表明,碳纳米管的加入能有效地提高粘结剂的结晶度和热稳定性,进而改善生坯在脱脂时的保形性.碳纳米管与粘结剂的非共价键结合有助于碳纳米管的均匀分散,更可能有利于复合材料成型后的脱脂.     

Polymers with cavities tuned for fast selective transport of small molecules and ions

Within a polymer film, free-volume elements such as pores and channels typically have a wide range of sizes and topologies. This broad range of free-volume element sizes compromises a polymer's ability to perform molecular separations. We demonstrated free-volume structures in dense vitreous polymers that enable outstanding molecular and ionic transport and separation performance that surpasses the limits of conventional polymers. The unusual microstructure in these materials can be systematically tailored by thermally driven segment rearrangement. Free-volume topologies can be tailored by controlling the degree of rearrangement, flexibility of the original chain, and judicious inclusion of small templating molecules. This rational tailoring of free-volume element architecture provides a route for preparing high-performance polymers for molecular-scale separations.