Electrochemical reduction of 1-([(4-halophenyl)imino]methyl)-2-naphthols in aprotic media.

The electrochemical reduction of 1-([(4-halophenyl)imino]methyl)-2-naphthols on graphite electrodes was studied using cyclic voltammetry, chronoamperometry, constant-potential coulometry and preparative constant-potential electrolysis techniques. The data revealed that the reduction on graphite was irreversible and followed an EC mechanism. The diffusion coefficients and the number of electrons transferred were determined using the chronoamperometric Cottrell slope and the ultramicro disc Pt-electrode steady-state current. The number of electrons was also determined by bulk electrolysis. The compounds were subjected to constant-potential preparative electrolysis and the electrolysis products were purified and identified by spectroscopic methods. Based on these findings, a mechanism for the electro-reduction process is proposed.     

Montgomery Multiplication in GF(2k)

We show that the multiplication operation c=a · b · r^-1 in the field GF(2^k can be implemented significantly faster in software than the standard multiplication, where r is a special fixed element of the field. This operation is the finite field analogue of the Montgomery multiplication for modular multiplication of integers. We give the bit-level and word-level algorithms for computing the product, perform a thorough performance analysis, and compare the algorithm to the standard multiplication algorithm in GF(2^k. The Montgomery multiplication can be used to obtain fast software implementations of the discrete exponentiation operation, and is particularly suitable for cryptographic applications where k is large.     

Phenol biosensor based on electrochemically controlled integration of tyrosinase in a redox polymer

An amperometric biosensor for the detection of phenolic compounds was developed based on the immobilization of tyrosinase within an Os-complex functionalized electrodeposition polymer. Integration of tyrosinase within the redox polymer assures efficient catechol recycling between the enzyme and the polymer bound redox sites. The non-manual immobilization procedure improves the reproducibility of fabrication process, greatly reduces the desorption of the enzyme from the immobilization layer, and, most importantly prevents fast inactivation of the enzyme by its substrate due to fast redox cycling. A two-layer sensor architecture was developed involving ascorbic acid oxidase entrapped within an electrodeposition polymer in a second layer on top of the redox polymer/tyrosinase layer. Using this sensor architecture it was possible to eliminate the current interference arising from direct ascorbate oxidation up to a concentration of 630 μM ascorbic acid. The effects of the polymer thickness, the enzyme/polymer ratio, and the applied potential were evaluated with respect to optimal sensor properties. The sensitivity of the optimized sensors for catechol was 6.1 nA μM⁻¹ with a detection limit of 10 nM, and for phenol 0.15 nA μM⁻¹ with a detection limit of 100 nM.     

Validation and verification of social processes within agent-based computational organization models

The use of simulation modeling in computational analysis of organizations is becoming a prominent approach in social science research. However, relying on simulations to gain intuition about social phenomena has significant implications. While simulations may give rise to interesting macro-level phenomena, and sometimes even mimic empirical data, the underlying micro and macro level processes may be far from realistic. Yet, this realism may be important to infer results that are relevant to existing theories of social systems and to policy making. Therefore, it is important to assess not only predictive capability but also explanation accuracy of formal models in terms of the degree of realism reflected by the embedded processes. This paper presents a process-centric perspective for the validation and verification (V&V) of agent-based computational organization models. Following an overview of the role of V&V within the life cycle of a simulation study, emergent issues in agent-based organization model V&V are outlined. The notion of social contract that facilitates capturing micro level processes among agents is introduced to enable reasoning about the integrity and consistency of agent-based organization designs. Social contracts are shown to enable modular compositional verification of interaction dynamics among peer agents. Two types of consistency are introduced: horizontal and vertical consistency. It is argued that such local consistency analysis is necessary, but insufficient to validate emergent macro processes within multi-agent organizations. As such, new formal validation metrics are introduced to substantiate the operational validity of emergent macro-level behavior. Levent Yilmaz is Assistant Professor of Computer Science and Engineering in the College of Engineering at Auburn University and co-founder of the Auburn Modeling and Simulation Laboratory of the M&SNet. Dr. Yilmaz received his Ph.D. and M.S. degrees from Virginia Polytechnic Institute and State University (Virginia Tech). His research interests are on advancing the theory and methodology of simulation modeling, agent-directed simulation (to explore dynamics of socio-technical systems, organizations, and human/team behavior), and education in simulation modeling. Dr. Yilmaz is a member of ACM, IEEE Computer Society, Society for Computer Simulation International, and Upsilon Pi Epsilon. URL: http://www.eng.auburn.edu/~yilmaz     

Effect of operating parameters on selective separation of heavy metals from binary mixtures via polymer enhanced ultrafiltration

Performance of continuous polymer enhanced ultrafiltration (PEUF) method was investigated for removal of mercury and cadmium from binary mixtures. This method includes the addition of polyethyleneimine (PEI) as a water soluble polymer to bind the metals, which was followed by ultrafiltration operation performed on both laboratory and pilot scale systems. The influence of various operating parameters such as temperature, metal/polymer ratio, presence of calcium ions and pH on retention of metals and permeate flux was investigated. To investigate the possibility of selective separation of mercury and cadmium, experiments were conducted for binary solutions at different pH and loading ratios. It was seen that the retention of mercury decreased and permeate flux increased when the temperature increased. The increased pH and decreased metal/polymer ratio, loading (L), resulted in higher retention of both metals. Shapes of retention vs. pH or L curves were very similar for both metals. Retentions stay almost constant at a value very close to unity until a critical L or pH value was reached, then, R decreases almost linearly with L or pH. However, retention of cadmium was affected more than that of mercury as the pH decreased and L increased. This leads to the selective separation of mercury and cadmium. At low pH values (about 5) and at high L values (about 0.3), mercury was removed by ultrafiltration operation while almost all cadmium passed through the membrane. At pH 5.5 and cadmium/polymer ratio about 0.35 and mercury/polymer ratio about 0.39, the highest separation factor was obtained as 49.     

Synthesis and characterization of a bifunctional amido-thiophene monomer and its copolymer with thiophene and electrochemical properties

A bifunctional amido-thiophene namely hexamethylene (bis-3-thiophene acetamide) (HMTA) was synthesized by the reaction of 3-thiophene acetic acid with hexamethylene diamine. Copolymerization in the presence of thiophene was achieved electrochemically in tetrabutylammonium tetrafluoroborate/acetonitrile (TBAFB/AN). Spectroelectrochemical analysis of the resulting copolymer [P(HMTA-co-Th)] reflected electronic transitions at 505 nm, 740 nm and ∼1000 nm, revealing π to π* transition, polaron and bipolaron band formation respectively. Switching ability was evaluated by a kinetic study via measuring the transmittance (%T) at the maximum contrast. Dual type polymer electrochromic devices (ECDs) based on P(HMTA-co-Th) and poly(ethylene dioxythiophene) (PEDOT) have been constructed. Spectroelectrochemistry, switching ability and stability of the devices were investigated by UV-vis spectroscopy and cyclic voltammetry. These devices exhibit low switching voltages (between 0.0 V and +1.6 V), short switching times with reasonable switching stability under atmospheric conditions.     

Synthesis,Characterization, and Thermal Investigation of Some Metal Complexes Containing Polydentate ONO-Donor Heterocyclic Schiff Base Ligand

Cu(II), Co(II), Ni(II), and Zn(II) metal complexes with new heterocyclic Schiff base derived from 1-amino-5-benzoyl-4-phenyl-1H-pyrimidine-2-one and 3-methoxysalicylaldehyde have been synthesized and characterized on the basis of elemental analyses, electronic, IR, and ¹H NMR spectra, and also by aid of molar conductivity measurements, magnetic moment measurements, and thermogravimetric analyses. It has been found that the Schiff base behaves as a neutral bidentate (NO) and tridentate (ONO) ligand forming chelates with 1 : 2 (metal : ligand) stoichiometry. Octahedral configuration is suggested for metal complexes. The conductivity data for the Ni(II) complexes are consistent with those expected for a 1 : 2 electrolyte.     

Conducting graft copolymers of poly(3‐methylthienyl methacrylate) with pyrrole and thiophene

A thiophene‐functionalized methacrylate monomer (3‐methylthienyl methacrylate) was synthesized via the esterification of 3‐thiophene methanol with methacryloyl chloride. The methacrylate monomer was polymerized by free‐radical polymerization in the presence of azobisisobutyronitrile as the initiator. Graft copolymers of poly(3‐methylthienyl methacrylate) (PMTM2) and polypyrrole and of PMTM2 and polythiophene were synthesized by constant‐potential electrolyses. p‐Toluene sulfonic acid, sodium dodecyl sulfate, and tetrabutylammonium tetrafluoroborate were used as the supporting electrolytes. PMTM2‐coated platinum electrodes were used as anodes in the polymerization of pyrrole and thiophene. Moreover, the oxidative polymerization of poly(3‐methylthienyl methacrylate) (PMTM1) was studied with FeCl₃ as the oxidant. The self‐polymerization of PMTM1 was also investigated by galvanostatic electrolysis both in dichloromethane and in propylene carbonate. The structures of PMTM1 and PMTM2 were investigated by several spectroscopic and thermal methods. The grafting process was elucidated with conductivity measurements, Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and scanning electron microscopy studies. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4131–4140, 2002     

5-Furan-2yl[1,3,4]oxadiazole-2-thiol, 5-furan-2yl-4H [1,2,4] triazole-3-thiol and their thiol-thione tautomerism

5-Furan-2-yl[1,3,4]oxadiazole-2-thiol (Ia) and 5-furan-2-yl-4H-[1,2,4]-triazole-3-thiol (Ib) were synthesized from furan-2-carboxylic acid hydrazide. Mannich bases and methyl derivatives were then prepared. The structures of the synthesized compounds were confirmed by elemental analyses, IR and (1)H-NMR spectra. Their thiol-thione tautomeric equilibrium is described.