Supramolecular structures of macromolecules containing bipyridine–copper(I) complexes as revealed from transmission electron microscopy studies

Transmission electron microscopy (TEM) studies on bipyridine (bpy) containing block copolymer systems showed the formation of nanoscopic polymer–ion complexes through complexation with copper(I) ions which segregated to highly ordered columnar domains of mesoscopic dimensions. The domains, i.e. stacks of [(bpy)₂Cu(I)] complex moieties could be visualized by complementary TEM techniques. First, electron energy loss spectra (EELS) showed the absorption edges of copper and nitrogen, which are specific for the bipyridine copper complexes. The element spectroscopic imaging (ESI) technique allowed the imaging of the net copper and net nitrogen distribution, and the coinciding pictures exhibited a microphase separated system in the case of a 3-block copolymer with complexed end segments. High resolution elastic bright field images showed interference lines with a line to line distance of about 8 A which could be related to the Cu–Cu distance in staggered Cu(I)–bipyridine complexes. Received: 6 August 1997 Accepted: 28 April 1998     

Deposition and characterization of Langmuir‐Blodgett films of cadmium arachidate/SWCNTs composites

The incorporation of single‐wall carbon nanotubes (SWCNTs) in cadmium arachidate film by means of the Langmuir‐Blodgett (LB) technique was investigated as a function of arachidic acid/SWCNT mass ratio at the air/water interface and in Langmuir‐Blodgett films. The behaviour at the air/water interface shows that SWCNTs act as an independent phase with respect to the cadmium arachidate. Deposition conditions are optimized when the weight ratio between the arachidic acid (AA) and SWCNTs is in the range 0.018:1 to 1:1. The general order of the LB multilayered structure was destroyed by the progressive density increase in SWCNT quantity as evidenced by X‐ray reflectivity (XRR) analysis. Scanning electron microscopy images indicated that when a multilayered structure was formed its layers consisted of SWCNT bundles stacked one over the other. Copyright © 2006 John Wiley & Sons, Ltd.     

电子探针定量分析的标准样品——几种多元氧化物单晶

在很高的温度和适宜的生长条件下,分别采用熔盐籽晶法和高温引上法生长了高质量的YAP、NAB、KTP、LN、BBO、SBN等多元氧化物单晶,它们具有优良的物理化学性能,严格的化学比,固定的组成与结构以及较好的化学均匀性和电子束轰击下的稳定性。广泛地用于激光和非线性光学领域。我们选用这些晶体为原材料研制电子探针定量分析的标准样品。经过测量和标定,这些单晶标样符合中华人民共和国国家标准GB 4930-85(电子探针显微分析标准样品通用技术条件)的规定。含有稀土元素的标样如NAB和YAP能发出绿色荧光,是电子显微术中理想的阴极发光材料。     

Synthesis of Molecular Wires of Linear and Branched Bis(terpyridine)‐Complex Oligomers and Electrochemical Observation of Through‐Bond Redox Conduction

Films of linear and branched oligomer wires of Fe(tpy)₂ (tpy=2,2′:6′,2′′‐terpyridine) were constructed on a gold‐electrode surface by the interfacial stepwise coordination method, in which a surface‐anchoring ligand, (tpy? C₆H₄N?NC₆H₄? S)₂ ( 1 ), two bridging ligands, 1,4‐(tpy)₂C₆H₄ ( 3 ) and 1,3,5‐(C?C? tpy)₃C₆H₃ ( 4 ), and metal ions were used. The quantitative complexation of the ligands and Fe^II ions was monitored by electrochemical measurements in up to eight complexation cycles for linear oligomers of 3 and in up to four cycles for branched oligomers of 4 . STM observation of branched oligomers at low surface coverage showed an even distribution of nanodots of uniform size and shape, which suggests the quantitative formation of dendritic structures. The electron‐transport mechanism and kinetics for the redox reaction of the films of linear and branched oligomer wires were analyzed by potential‐step chronoamperometry (PSCA). The unique current‐versus‐time behavior observed under all conditions indicates that electron conduction occurs not by diffusional motion but by successive electron hopping between neighboring redox sites within a molecular wire. Redox conduction in a single molecular wire in a redox‐polymer film has not been reported previously. The analysis provided the rate constant for electron transfer between the electrode and the nearest redox‐complex moiety, k₁ (s^?1), as well as that for intrawire electron transfer between neighboring redox‐complex moieties, k₂ (cm² mol^?1 s^?1). The strong effect of the electrolyte concentration on both k₁ and k₂ indicates that the counterion motion limits the electron‐hopping rate at lower electrolyte concentrations. Analysis of the dependence of k₁ and k₂ on the potential gave intrinsic kinetic parameters without overpotential effects: k₁⁰=110 s^?1, k₂⁰=2.6×10¹² cm² mol^?1 s^?1 for [n Fe 3 ], and k₁⁰=100 s^?1, k₂⁰=4.1×10¹¹ cm² mol^?1 s^?1 for [n Fe 4 ] (n=number of complexation cycles).     

Investigations of precipitates in heat treated AgPd30/CuSn6 layers

The subject of the investigations are precipitation zones, which grew as a result of chemical diffusion in AgPd30/CuSn6 bimetals. These precipitation zones have been characterized by metallography, electron probe microanalysis and x-ray diffraction. The growth of precipitation zones in the plating layer and in the substrate layer in dependence on time have been determined. The use of x-ray diffraction alone for the identification of the precipitates could not supply satisfying results in every case. This problem was solved by the application of electron probe microanalysis using a correction method, which allows the estimation of the chemical composition of small particles.Dedicated to Professor Dr. rer. nat. Dr. h. c. Hubertus Nickel on the occasion of his 65th birthday     

Photo-induced Charge Separation of p-Tricyanovinyl-N,N-Dialkylanilines

In this paper,p-tricyanovinyl-N,N-dialkylanilines were synthesized as model compounds and through their spectroscopic behavior,the photo-induced electron transfer,charge separation were discussed and the aggregation in DMSO-H_2O system was investigated.     

Two-photon absorption in quadrupolar pi-conjugated molecules: influence of the nature of the conjugated bridge and the donor-acceptor separation

Quadrupolar-type substitution of pi-conjugated chromophores with donor and acceptor groups has been shown to increase their two-photon absorption (TPA) response by up to two orders of magnitude. Here, we apply highly correlated quantum-chemical calculations to evaluate the impact of the nature of conjugated bridge and the charge-transfer distance on that enhancement. We compare chromophores with phenylenevinylene-, thienylenevinylene-, polyene-, and indenofluorene-type backbones substituted by dimethylamino and cyano groups. In all compounds, we find a strongly TPA-active A(g) state (either 2A(g) or 3A(g)) in the low-energy region, as well as a higher lying TPA-active state (mA(g)) at close to twice the energy of the lowest lying one-photon allowed state; the smaller energy detuning in the mA(g) states results in very large TPA cross sections delta. We also investigate the influence of the degree of ground-state polarization on TPA. Independent of the nature of the backbone and the donor-acceptor separation, delta displays the same qualitative evolution with a maximum before the cyanine-like limit; the highest TPA cross sections are calculated for distirylbenzene- and polyene-based systems.     

Formation of Negative Hydrogen Ions in a Ne–H2 Hollow Cathode Discharge

The formation of negative hydrogen ions in a conventional hollow cathode discharge has been investigated. A mixture of Ne and H₂ proved to be more advantageous compared to pure hydrogen. The study has been performed by solving the electron Boltzmann equation, coupled with a system of balance equations for neon and hydrogen neutral and charged particles. The vibrational distribution function of hydrogen has been calculated. Our calculations show unusually high population of vibrationally excited hydrogen molecules in a Ne–H₂ mixture, which explains the high density of negative hydrogen ions under optimal conditions (total gas pressure of few Torr, hydrogen number mole fraction of 1–10% and discharge current of 10–100 mA). Line intensities originating from highly excited neon states vs. hydrogen pressure have been calculated and a comparison with existing experimental results has been made.     

激光诱导等离子体中的电子密度和电子温度的测量

脉冲激光诱发等离子体的谱诊断技术用来对其电子密度和电子温度的测量结果与理论计算进行了比较，同时讨论了运用这个方法的物理条件．