Synthesis of chiral ferrosalen ligands and their applications in asymmetric catalysis

A new series of chiral ferrosalen ligands was designed and synthesized. The special feature of the ferrosalen ligands is that the chirality originated from the planar chiral ferrocenyl structure. For most known salen ligands, chirality comes from central and axial chiral centers. The key building block for the construction of these ferrosalen ligands was synthesized stereoselectively by a chiral auxiliary approach. This approach does not consume any chiral material, and does not require chiral HPLC resolution. Using this method, nine ligands were prepared using ferrocene as the starting material. In addition, the steric hindrance was modulated by changing the cyclopentadienyl group to the more bulky pentamethylcyclopentadienyl- and pentaphenylcyclopentadienyl- groups. The structure of these ligands was established by 1H and 13C NMR. The structure of a ferrosalen-Cu (II) complex was determined by single crystal X-ray diffraction analysis. All the chiral ferrosalen ligands were tested in catalytic asymmetric reactions including enantioselective carbonyl-ene reaction, enantioselective Strecker-type reaction and enantioselective silylcyanation. For the carbonyl-ene reaction, up to 99% yield and 29% enantiomeric excess (ee) were obtained using ligand-Co (III) as the catalysts; For the Strecker-type reaction, a maximum of 20% ee was obtained using ligand-AlCl as the catalyst; For the silylcyanation reaction, up to 99% yield and 26% ee were obtained using ligand-AlCl as the catalyst.

Development and testing of an asymmetric capacitor with a nickel-carbon foam positive electrode

Electrochemical capacitors (ECs), also known as supercapacitors or ultracapacitors, are energy storage devices with properties between batteries and conventional capacitors. EC have evolved through several generations. The trend in EC is to combine a double-layer electrode with a battery-type electrode in an asymmetric capacitor configuration. The double-layer electrode is usually an activated carbon (AC) since it has high surface area, good conductivity, and relatively low cost. The battery-type electrode usually consists of PbO2 or Ni(OH)2. In this research, a graphitic carbon foam was impregnated with Co-substituted Ni(OH)2 using electrochemical deposition to serve as the positive electrode in the asymmetric capacitor. The purpose was to reduce the cost and weight of the ECs while maintaining or increasing capacitance and gravimetric energy storage density. The XRD result indicated that the nickel-carbon foam electrode was a typical α-Ni(OH)2. The specific capacitance of the nickel-carbon foam electrode was 2641 F/g at 5 mA/cm2, higher than the previously reported value of 2080 F/g for a 7.5% Al-substituted α-Ni(OH)2 electrode. Three different ACs (RP-20, YP-50F, and Ketjenblack EC-600JD) were evaluated through their morphology and electrochemical performance to determine their suitability for use in ECs. The study indicated that YP-50F demonstrated the better overall performance because of the combination of micropore and mesopore structures. Therefore, YP-50F was chosen to combine with the nickel-carbon foam electrode for further evaluation. Six cells with different mass ratios of negative to positive active mass were fabricated to study the electrochemical performance. Among the different mass ratios, the asymmetric capacitor with the mass ratio of 3.71 gave the highest specific energy and specific power, 24.5 W.h/kg and 498 W/kg, respectively.

Performance evaluation of a novel asymmetric capacitor using a light-weight, carbon foam supported nickel electrode

Electrochemical capacitors have been an important development in recent years in the field of energy storage. Capacitors can be developed by utilizing either double layer capacitance at the electrode/solution interfaces alone or in combination with a battery electrode associated with a faradic redox process in one electrode. An asymmetric capacitor consisting of electrochemically deposited nickel hydroxide, supported on carbon foam as a positive electrode and carbon sheet as a negative electrode has been successfully assembled and cycled. One objective of this study has been to demonstrate the viability of the nickel carbon foam positive electrode, especially in terms of cycle life. Electrochemical characterization shows stable, high cycle performance in 26 wt. % KOH electrolyte with a maximum energy density of 4.1 Wh/Kg and a relaxation time constant of 6.24 s. This cell has demonstrated high cycle life, 14,500 cycles, with efficiency better than 98%. In addition, the cell failure mechanism and self-discharge behavior of the aforesaid capacitor are analyzed.

Exact Solutions to the Symmetric and Asymmetric Vehicle Routing Problem with Simultaneous Delivery and Pick-Up

In reverse logistics networks, products (e.g., bottles or containers) have to be transported from a depot to customer locations and, after use, from customer locations back to the depot. In order to operate economically beneficial, companies prefer a simultaneous delivery and pick-up service. The resulting Vehicle Routing Problem with Simultaneous Delivery and Pick-up (VRPSDP) is an operational problem, which has to be solved daily by many companies. We present two mixed-integer linear model formulations for the VRPSDP, namely a vehicle-flow and a commodity-flow model. In order to strengthen the models, domain-reducing preprocessing techniques, and effective cutting planes are outlined. Symmetric benchmark instances known from the literature as well as new asymmetric instances derived from real-world problems are solved to optimality using CPLEX 12.1.

Asymmetric Effects of Loss and Gain of a Floral Trait on Pollinator Preference

Shifts in pollination syndromes involve coordinated changes in multiple floral traits. This raises the question of how plants can cope with rapid changes in pollinator availability by the slow process of accumulation of mutations in multiple genes. Here we study the transition from bee to hawkmoth pollination in the genus Petunia. Interspecific crosses followed by single locus introgressions were used to recreate putative intermediate evolutionary stages in the evolution of moth pollination. The effect of the loss/gain of petal color was asymmetric: it had no influence on the established pollinator but enhanced visitation by the new pollinator. Therefore, shifts in pollination syndromes may proceed through intermediate stages of reduced specialization and consequently enhanced reproductive assurance. The loss of petal color in moth-pollinated Petunia involves null mutations in a single regulatory gene, An2. Such simple genetic changes may be sufficiently rapid and frequent to ensure survival during pollinator failure.

Conservative treatment of asymmetric ankle osteoarthritis

This review article summarizes the currently available (poor) evidence of conservative treatment of asymmetric ankle osteoarthritis in the literature and adds the authors' experience with the particular technique. The use of dietary supplementation, viscosupplementation, platelet-rich plasma, nonsteroidal anti-inflammotory drugs, corticosteroid injections, physical therapy, shoe modifications and orthoses, and patient's education in asymmetric ankle osteoarthritis is outlined. There definitively is a place for conservative treatment with reasonable success in patients whose ankles do not qualify anymore for joint-preserving surgery and in patients with medical or orthopedic contraindications for realignment surgery, total ankle replacement, and ankle arthrodesis.

Asymmetric cyclopropanation of olefins catalysed by Cu(I) complexes of chiral pyridine-containing macrocyclic ligands (Pc-L*)

The synthesis and characterisation of copper(I) complexes of chiral pyridine-containing macrocyclic ligands (Pc-L*) and their use as catalysts in asymmetric cyclopropanation reactions are reported. All ligands and metal complexes were fully characterised, including crystal structures of some species determined by X-ray diffraction on single crystals. This allowed characterising the very different conformations of the macrocycles which could be induced by different substituents or by metal complexation. The strategy adopted for the ligand synthesis is very flexible allowing several structural modifications. A small library of macrocyclic ligands possessing the same donor properties but with either C-1 or C-2 symmetry was synthesized. Cyclopropane products with both aromatic and aliphatic olefins were obtained in good yields and enantiomeric excesses up to 99%.

Measuring the bending of asymmetric planar EAP structures

The geometric characterization of low-voltage dielectric electro-active polymer (EAP) structures, comprised of nanometer thickness but areas of square centimeters, for applications such as artificial sphincters requires methods with nanometer precision. Direct optical detection is usually restricted to sub-micrometer resolution because of the wavelength of the light applied. Therefore, we propose to take advantage of the cantilever bending system with optical readout revealing a sub-micrometer resolution at the deflection of the free end. It is demonstrated that this approach allows us to detect bending of rather conventional planar asymmetric, dielectric EAP-structures applying voltages well below 10 V. For this purpose, we built 100 μm-thin silicone films between 50 nm-thin silver layers on a 25 μm-thin polyetheretherketone (PEEK) substrate. The increase of the applied voltage in steps of 50 V until 1 kV resulted in a cantilever bending that exhibits only in restricted ranges the expected square dependence. The mean laser beam displacement on the detector corresponded to 6 nm per volt. The apparatus will therefore become a powerful mean to analyze and thereby improve low-voltage dielectric EAP-structures to realize nanometer-thin layers for stack actuators to be incorporated into artificial sphincter systems for treating severe urinary and fecal incontinence.

Salience and Asymmetric Judgments of Physical Distance

Previous research has shown that distance estimates made from memory are often asymmetric. Specifically, when A is a prominent location (a land-mark) and B is not, people tend to recall a longer distance from A to B than from B to A. Results of two experiments showed that asymmetric judgments of distance are not restricted to judgments made from memory but occur also for judgments made when all relevant visual cues are still present. Furthermore, results indicated that situational salience is sufficient to produce asymmetric judgments and that distinctiveness (such as in the case of architectural landmarks) is not necessary.

Concise Asymmetric Synthesis and Pharmacological Characterization of All Stereoisomers of Glutamate Transporter Inhibitor TFB-TBOA and Synthesis of EAAT Photoaffinity Probes

Glutamate is the major excitatory neurotransmitter in the mammalian brain. Its rapid clearance after the release into the synaptic cleft is vital in order to avoid toxic effects and is ensured by several transmembrane transport proteins, so-called excitatory amino acid transporters (EAATs). Impairment of glutamate removal has been linked to several neurodegenerative diseases and EAATs have therefore received increased attention as therapeutic targets. O-benzylated L-threo-β-hydroxyaspartate derivatives have been developed previously as highly potent inhibitors of EAATs with TFB-TBOA ((2S,3S)-2-amino-3-((3-(4-(trifluoromethyl)benzamido)benzyl)oxy)succinic acid) standing out as low-nanomolar inhibitor. We report the stereoselective synthesis of all four stereoisomers of TFB-TBOA in less than a fifth of synthetic steps than the published route. For the first time, the inhibitory activity and isoform selectivity of these TFB-TBOA enantio- and diastereomers were assessed on human glutamate transporters EAAT1-3. Furthermore, we synthesized potent photoaffinity probes based on TFB-TBOA using our novel synthetic strategy.

Capital Accumulation in the Presence of Informal Credit Contracts: Does the Incentive Mechanism Work Better than Credit Rationing Under Asymmetric Information?

Credit markets with asymmetric information often prefer credit rationing as a profit maximizing device. This paper asks whether the presence of informal credit markets reduces the cost of credit rationing, that is, whether it can alleviate the impact of asymmetric information based on the available information. We used a dynamic general equilibrium model with heterogenous agents to assess this. Using Indian credit market data our study shows that the presence of informal credit market can reduce the cost of credit rationing by separating high risk firms from the low risk firms in the informal market. But even after this improvement, the steady state capital accumulation is still much lower as compared to incentive based market clearing rates. Through self revelation of each firm's type, based on the incentive mechanism, banks can diversify their risk by achieving a separating equilibrium in the loan market. The incentive mechanism helps banks to increase capital accumulation in the long run by charging lower rates and lending relatively higher amount to the less risky firms. Another important finding of this study is that self-revelation leads to very significant welfare improvement, as measured by consumptiuon equivalence.

Antidumping as Strategic Trade Policy Under Asymmetric Information

In the last two decades, trade liberalization under GATT/WTO has been partly offset by an increase in antidumping protection. Economists have argued convincingly that this is partly due to the inclusion of sales below cost in the definition of dumping during the GATT Tokyo Round. The introduction of the cost- based dumping definition gives regulating authorities a better opportunity to choose protection according to their liking. This paper investigates the domestic government's antidumping duty choice in an asymmetric information framework where the foreign firm's cost is observed by the domestic firm, but not by the government. To induce truthful revelation, the government can design a tariff schedule, contingent on firms' cost reports, accompanied by a threat to collect additional information for report verification (i.e., auditing) and, in case misreporting is detected, to set penalty duties. We show that depending on the concrete assumptions, the domestic government may not only be able to extract the true cost information, but also succeeds in implementing the full-information, governmental welfare-maximizing duty. In this case, the antidumping framework within GATT/WTO does not only offer the means to pursue strategic trade policy disguised as fair trade policy, but it also helps overcome the informational problems with regard to correctly determining the optimal strategic trade policy.

Asymmetric Information, Tax Evasion and Alternative Instruments of Government Revenue

Using a pure-exchange overlapping generations model, characterized with tax evasion and information asymmetry between the government (the social planner) and the financial intermediaries, we try and seek for the optimal tax and seigniorage plans, derived from the welfare maximizing objective of the social planner. We show that irrespective of whether the economy is characterized by tax evasion, or asymmetric information, a benevolent social planner, maximizing welfare and simultaneously financing the budget constraint, should optimally rely on explicit rather than implicit taxation.