Investigation of ion-bombarded conducting polymer films by scanning electrochemical microscopy (SECM)

Scanning electrochemical microscopy (SECM) was used to investigate the effect of ion bombardment on thin films of the conducting polymers poly[3-ethoxy-thiophene] (PEOT) and poly[ethylenedioxy-thiophene] (PEDT). Bombardment with Ar⁺-ions converts the topmost 30 nm thick layer to an essentially insulating material. SECM approach curves as well as two dimensional scans prove the existence of regions of different conductivity within the irradiated regions that did not show a significant dependence on ion dosage. PEDT layers patterned by ion bombardment through microscopic masks are investigated as prototypes of miniaturized printed circuit boards that can be formed by galvanic copper deposition onto conducting PEDT. Defects in conducting polymer patterns were analyzed by SECM imaging before any deposition of copper. Appropriate representations of SECM images for the evaluation of this technologically important question are discussed.     

Investigation of free base, Mg, Sn, and Zn substituted porphyrin LB films as gas sensors for organic analytes

The visible absorption spectra of various substituted porphyrin compounds both in chloroform solution and as Langmuir-Blodgett (LB) solid-state films have been investigated. The porphyrin compounds examined were the Zn, Sn, Mg, and free base derivatives of 5,10,15,20-tetrakis[3,4-bis(2-ethylhexyloxy)phenyl]-21H,23H-porphine (EHO). Changes in the absorption spectra of these materials induced by their exposure to various organic compounds are reported with a view toward determining whether this is a useful approach toward an optical gas sensor.     

Catalytic Activation of Imines by Chalcogen Bond Donors in a Povarov [4+2] Cycloaddition Reaction

Recently, chalcogen bonding has been investigated in more detail in organocatalysis and the scope of activated functionalities continues to increase. Herein, the activation of imines in a Povarov [4+2] cycloaddition reaction with bidentate cationic chalcogen bond donors is presented. Tellurium-based Lewis acids show superior properties compared to selenium-based catalysts and inactive sulfur-based analogues. The catalytic activity of the chalcogen bonding donors increases with weaker binding anions. Triflate, however, is not suitable due to its participation in the catalytic pathway. A solvent screening revealed a more efficient activation in less polar solvents and a pronounced effect of solvent (and catalyst) on endo : exo diastereomeric ratio. Finally, new chiral chalcogen bonding catalysts were applied but provided only racemic mixtures of the product.     

Epi-convergence Properties of Smoothing by Infimal Convolution

This paper concerns smoothing by infimal convolution for two large classes of functions: convex, proper and lower semicontinous as well as for (the nonconvex class of) convex-composite functions. The smooth approximations are constructed so that they epi-converge (to the underlying nonsmooth function) and fulfill a desirable property with respect to graph convergence of the gradient mappings to the subdifferential of the original function under reasonable assumptions. The close connection between epi-convergence of the smoothing functions and coercivity properties of the smoothing kernel is established.     

Sets of Type (a, b) From Subgroups of ΓL(1, pR)

In this paper k-sets of type (a, b) with respect to hyperplanes are constructed in finite projective spaces using powers of Singer cycles. These are then used to construct further examples of sets of type (a, b) using various disjoint sets. The parameters of the associated strongly regular graphs are also calculated. The construction technique is then related to work of Foulser and Kallaher classifying rank three subgroups of AL(1, p ^R). It is shown that the sets of type (a, b) arising from the Foulser and Kallaher construction in the case of projective spaces are isomorphic to some of those constructed in the present paper.     

Recovery of organic acids from fermentation broths

Rising concerns over the use of fossil resources have generated renewed interest in the production of commodity chemicals via fermentation. Organic acids are a particularly attractive target because their functionality enables downstream catalytic upgrading to a variety of compounds. In this article, we survey how common technical issues are addressed in the recovery schemes for several organic acids. We present results for the recovery of acetate using a new method based on amine complexation. Our reactive separation scheme produces a high-purity product, is energy efficient, and avoids the coproduction of a waste salt coproduct, all prerequisites for a large-scale production process.     

Maximally aligned states in 99Ag

Excited states of ⁹⁹Ag were populated via the ⁵⁰Cr + ⁵⁸Ni (261 MeV) reaction using the NORDBALL detector array equipped with charged-particle and neutron detector systems for reaction channel separation. On the basis of the measured γγ-coincidence relations and angular distribution ratios a significantly extended level scheme has been constructed up to E _x ∼ 7.8 MeV and I = 35/2. The experimental results were described within the framework of the shell model. Candidates for states fully aligned in the πg _9/2 ^-3ν(d _5/2, g _7/2)² valence configuration space were found at 4109 and 6265 keV. Received: 18 June 2002 / Accepted: 11 October 2002 / Published online: 4 February 2003 RID="a" ID="a"e-mail: sohler@atomki.hu Communicated by J. ?yst?     

Free-carrier absorption modulation in silicon nanocrystal slot waveguides

Free-carrier absorption (FCA) has proven to be an important obstacle in the development of a silicon-based laser; however, FCA may serve as a potential advantage in active silicon-based switches or modulators. In this work, we present FCA modulation in slot waveguides with silicon nanocrystals (Si-ncs) embedded in SiO(2) as the low-index slot material. Slot waveguides were fabricated with and without Si-ncs, and the presence of Si-ncs was shown to increase the pump-induced FCA loss in the waveguides by a factor of 4.5. We modeled the Si-nc material using a four-level rate equation analysis to estimate the excited population of Si-ncs, allowing us to extract a value of 2.6 × 10(-17) cm(2) for the FCA cross section of the Si-nc material.     

Lagrangian and Eulerian models for simulating turbulent dispersion and coalescence of droplets within a spray

Lagrangian and Eulerian modelling approaches are compared for simulating turbulent dispersion and coalescence of droplets within a spray. Both models predict similar droplet dispersion rates and shifts in droplet size distribution due to coalescence within the spray, over a wide range of droplet and gas flows, and for sprays with different droplet-size distributions at the nozzle exit. The computer time required for simulating coalescence within a steady axisymmetric spray is of a similar order of magnitude regardless of which formulation, Eulerian or Lagrangian, is adopted. However, the Lagrangian formulation is more practical in terms of the range of applicability and ease of implementation.     

Using delta15N and delta18O to evaluate the sources and pathways of NO3- in rainfall event discharge from drained agricultural grassland lysimeters at high temporal resolutions

The origin of NO(3) (-) yielded in drainage from agricultural grasslands is of environmental significance and has three potential sources; (i) soil organic mater (SOM), (ii) recent agricultural amendments, and (iii) atmospheric inputs. The variation in delta(15)N-NO(3) (-) and delta(18)O-NO(3) (-) was measured from the 'inter-flow' and 'drain-flow' of two 1 ha drained lysimeter plots, one of which had received an application of 21 m(3) of NH(4) (+)-N-rich agricultural slurry, during two rainfall events. Drainage started to occur 1 month after the application of slurry. The concentrations of NO(3) (-)-N from the two lysimeters were comparable; an initial flush of NO(3) (-)-N occurred at the onset of drainage from both lysimeters before levels quickly dropped to <1 mg NO(3) (-)-N L(-1). The isotopic signature of the delta(15)N-NO(3) (-) and delta(18)O-NO(3) (-) during the first two rainfall events showed a great deal of variation over short time-periods from both lysimeters. Isotopic variation of delta(15)N-NO(3) (-) during rainfall events ranged between -1.6 to +5.2 per thousand and +0.4 to +11.1 per thousand from the inter-flow and drain-flow, respectively. Variation in the delta(18)O-NO(3) (-) ranged from +2.0 to +7.8 per thousand and from +3.3 to +8.4 per thousand. No significant relationships between the delta(15)N-NO(3) (-) or delta(18)O-NO(3) (-) and flow rate were observed in most cases although delta(18)O-NO(3) (-) values indicated a positive relationship and delta(15)N-NO(3) (-) values a negative relationship with flow during event 2. Data from a bulked rainfall sample when compared with the theoretical delta(18)O-NO(3) (-) for soil microbial NO(3) (-) indicated that the contribution of rainfall NO(3) (-) accounted for 8% of the NO(3) (-) in the lysimeter drainage at most. The calculated contribution of rainfall NO(3) (-) was not enough to account for the depletion in delta(15)N-NO(3) (-) values observed during the duration of the rainfall event 2. The relationship between delta(15)N-NO(3) (-) and delta(18)O-NO(3) (-) from the drain-flow indicated that denitrification was causing enrichment in the isotopes from this pathway. The presence of slurry seemed to cause a relative depletion in delta(18)O-NO(3) (-) in the inter-flow and delta(15)N-NO(3) (-) in the drain-flow compared with the zero-slurry lysimeter. This may have been caused by increased microbial nitrification stimulated by the presence of increased NH(4) (+)-N.