Correlation of the EPR properties of perchlorotriphenylmethyl radical and their efficiency as DNP polarizers

Water soluble perchlorinated trityl (PTM) radicals were found to be effective 95 GHz DNP (dynamic nuclear polarization) polarizers in ex situ (dissolution) 13C DNP (Gabellieri et al., Angew Chem., Int. Ed. 2010, 49, 3360). The degree of the nuclear polarization obtained was reported to be dependent on the position of the chlorine substituents on the trityl skeleton. In addition, on the basis of the DNP frequency sweeps it was suggested that the 13C NMR signal enhancement is mediated by the Cl nuclei. To understand the DNP mechanism of the PTM radicals we have explored the 95 GHz EPR characteristics of these radicals that are relevant to their performance as DNP polarizers. The EPR spectra of the radicals revealed axially symmetric g-tensors. A comparison of the spectra with the 13C DNP frequency sweeps showed that although the solid effect mechanism is operational the DNP frequency sweeps reveal some extra width suggesting that contributions from EPR forbidden transitions involving 35,37Cl nuclear flips are likely. This was substantiated experimentally by ELDOR (electron-electron double resonance) detected NMR measurements, which map the EPR forbidden transitions, and ELDOR experiments that follow the depolarization of the electron spin upon irradiation of the forbidden EPR transitions. DFT (density functional theory) calculations helped to assign the observed transitions and provided the relevant spin Hamiltonian parameters. These results show that the 35,37Cl hyperfine and nuclear quadrupolar interactions cause a considerable nuclear state mixing at 95 GHz thus facilitating the polarization of the Cl nuclei upon microwave irradiation. Overlap of Cl nuclear frequencies and the 13C Larmor frequency further facilitates the polarization of the 13C nuclei by spin diffusion. Calculation of the 13C DNP frequency sweep based on the Cl nuclear polarization showed that it does lead to an increase in the width of the spectra, improving the agreement with the experimental sweeps, thus supporting the existence of a new heteronuclear assisted DNP mechanism.

Balancing effluent quality, economic cost and greenhouse gas emissions during the evaluation of (plant-wide) control/operational strategies in WWTPs

The objective of this paper was to show the potential additional insight that result from adding greenhouse gas (GHG) emissions to plant performance evaluation criteria, such as effluent quality (EQI) and operational cost (OCI) indices, when evaluating (plant-wide) control/operational strategies in wastewater treatment plants (WWTPs). The proposed GHG evaluation is based on a set of comprehensive dynamic models that estimate the most significant potential on-site and off-site sources of CO2, CH4 and N2O. The study calculates and discusses the changes in EQI, OCI and the emission of GHGs as a consequence of varying the following four process variables: (i) the set point of aeration control in the activated sludge section; (ii) the removal efficiency of total suspended solids (TSS) in the primary clarifier; (iii) the temperature in the anaerobic digester; and (iv) the control of the flow of anaerobic digester supernatants coming from sludge treatment. Based upon the assumptions built into the model structures, simulation results highlight the potential undesirable effects of increased GHG production when carrying out local energy optimization of the aeration system in the activated sludge section and energy recovery from the AD. Although off-site CO2 emissions may decrease, the effect is counterbalanced by increased N2O emissions, especially since N2O has a 300-fold stronger greenhouse effect than CO2. The reported results emphasize the importance and usefulness of using multiple evaluation criteria to compare and evaluate (plant-wide) control strategies in a WWTP for more informed operational decision making

Efficiency and environmental regulation: a 'complex situation'

Production of desirable outputs is often accompanied by undesirable by products that have damaging effects on the environment, and whose disposal is frequently regulated by public authorities. In this paper, we compute directional technology distance functions under particular assumptions concerning disposability of bads in order to test for the existence of what we call ‘complex situations’, where the biggest producer is not the greatest polluter. Furthermore, we show that how in such situations, environmental regulation could achieve an effective reduction in the aggregate level of bad outputs without reducing the production of good outputs. Finally, we illustrate our methodology with an empirical application to a sample of Spanish tile ceramic producers.

Efficiency and quality in local government management: the case of Spanish local authorities

This study analyses efficiency levels in Spanish local governments and their determining factors through the application of DEA (Data Envelopment Analysis) methodology. It aims to find out to what extent inefficiency arises from external factors beyond the control of the entity, or on the other hand, how much it is due to inadequate management of productive resources. The results show that on the whole, there is still a wide margin within which managers could increase local government efficiency levels, although it is revealed that a great deal of inefficiency is due to exogenous factors. It is specifically found that the size of the entity, per capita tax revenue, the per capita grants or the amount of commercial activity are some of the factors determining local government inefficiency.

Consumption externalities, habit formation, and equilibrium efficiency

We analyze the welfare properties of the competitive equilibrium in a capital accumulation model where individual preferences are subjected to both habit formation and consumption spillovers. We also discuss how consumption externalities and habits interact to generate an inefficient dynamic equilibrium. Finally, we characterize optimal tax policies aimed to restore efficient decentralized paths.

A dual characterization of incentive efficiency

We show that incentive efficient allocations in economies with adverse selection and moral hazard can be determined as optimal solutions to a linear programming problem and we use duality theory to obtain a complete characterization of the optima. Our dual analysis identifies welfare effects associated with the incentives of the agents to truthfully reveal their private information. Because these welfare effects may generate non-convexities, incentive efficient allocations may involve randomization. Other properties of incentive efficient allocations are also derived.

Allocative and productive efficiency in REE with asymetric information

We characterize the divergence between informational and economic efficiency in a rational expectations competitive market with asymmetric information about the costs of production. We find that prices may contain too much or too little information with respect to incentive efficient allocations depending on whether the main role of the price is, respectively, the traditional as index of scarcity or informational. Only when REE degenerate to Cournot equilibria the market solution does not show llocative inefficiency. With multidimensional uncertainty we find that the REE price does not have in general the incentive efficient information mix: It pays to sacrifice allocative efficiency at the REE to improve productive efficiency.

Public enterprise reforms and efficiency in regulated environments: the case of the postal sector

Purpose - This paper focuses on analyzing the effect that public reforms have on the efficiency of state-owned enterprises in regulated environments. Design/methodology/approach - The research is focused in the postal sector where public and private companies must obey a legal framework related to provide a universal service. The analysis is carried out using a panel of 7 European postal operators for the period 1997-2003. The activity analyzed was the letter mail division; we take as key variable the unit cost of a letter and use a translog cost function where as independent variables we include traffic levels, labor cost per employee, quality and availability of the service as well as the type of ownership (public or private). Additionally, in a second stage the geographical differences among countries are considered. Findings - Results indicate that postal operators that experienced organizational changes without being privatized, such as the Spanish and Greek operators, do not have higher unit costs than privatized postal operators like the one of Germany and the Netherlands. Moreover, we find that in all cases the operator of Ireland appear to be the most efficient. In this case restructuring process has been carried out giving an important leadership role to workers. This suggests us that labor culture could be a key variable to study when analyzing reform processes in public enterprises. Originality/value - Our findings show that in a regulated environment like in the postal sector, public and private companies can obtain similar efficiency levels in term of unit costs.

Cooperative production and efficiency

We characterize the sharing rule for which a contribution mechanism achieves efficiency in a cooperative production setting when agents are heterogeneous. The sharing rule bears no resemblance to those considered by the previous literature. We also show for a large class of sharing rules that if Nash equilibrium yields efficient allocations, the production function displays constant returns to scale, a case in which cooperation in production is useless.

The Appraisal of projects with environmental impacts. Efficiency and Sustainability

It is usually assumed that the appraisal of the impacts experienced by present generations does not entail any difficulty. However, this is not true. Moreover, there is not a widely accepted methodology for taking these impacts into account. Some of the controversial issues are: the appropriate value for the discount rate, the choice of the units for expressing the impacts, physical or monetary units -income, consumption or investment- and the valuation of tangible and intangible goods. When approaching the problem of very long term impacts, there is also the problem of valuing the impacts experienced by future generations, through e.g., the use of an intergenerational discount rate. However, if this were the case, the present generation perspective would prevail, as if all the property rights on the resources were owned by them. Therefore, the sustainability requirement should also be incorporated into the analysis. We will analyze these problems in this article and show some possible solutions.

Organisational status and efficiency: the case of the spanish SOE "Paradores"

The purpose of this paper is to provide new evidence on the issue of the effect on public enterprises economic performance of the introduction of some given changes in organisational status and management practices, while keeping the enterprises under public control. Our approach is case study type and relies on comparative efficiency literature. We identify relevant changes on the organisational status of a State owned large hotel group along a period of twenty years, next we measure its annual efficiency indicators, and then evaluate to which extent the observed changes in economic performance can be attributable to the corresponding management reforms carried out. As a result we find that the formally more relevant change in organisational status (the enterprise passing to be a Limited Company), which implied a substantial increase in the enterprise autonomy, did not produce a significant improvement in its economic performance; a finding contrary to what we expected according to agency theory. However, a second relevant organisational change –five years later- when both the principal (government) and the agent (firm’s CEO) changed is consistently related to a significant improvement in economic performance. As a research implication we abide for use more precise agency theory statements; and as a practical implication we argue here that potentialities of improvement brought about by a formal-legal change in the status of the enterprise may require also –in order to actually improve firm’s efficiency- some changes in the firm’s key personal positions: supervisor (principal) and CEO (agent), in the sense that a change to a greater-autonomy for the enterprise it seems should come together a parallel new ‘management culture’. Practical implications Management good practises to apply to other public enterprise’s restructuring in order to improve their efficiency. It’s the first study on organizational changes and efficiency for an important Spanish public enterprise.

Productive efficiency and regulatory reform: The case of vehicle inspection services

Measuring productive efficiency provides information on the likely effects of regulatory reform. We present a Data Envelopment Analysis (DEA) of a sample of 38 vehicle inspection units under a concession regime, between the years 2000 and 2004. The differences in efficiency scores show the potential technical efficiency benefit of introducing some form of incentive regulation or of progressing towards liberalization. We also compute scale efficiency scores, showing that only units in territories with very low population density operate at a sub-optimal scale. Among those that operate at an optimal scale, there are significant differences in size; the largest ones operate in territories with the highest population density. This suggests that the introduction of new units in the most densely populated territories (a likely effect of some form of liberalization) would not be detrimental in terms of scale efficiency. We also find that inspection units belonging to a large, diversified firm show higher technical efficiency, reflecting economies of scale or scope at the firm level. Finally, we show that between 2002 and 2004, a period of high regulatory uncertainty in the sample’s region, technical change was almost zero. Regulatory reform should take due account of scale and diversification effects, while at the same time avoiding regulatory uncertainty.

Bargaining one-dimensional policies and the efficiency of super majority rules

We consider negotiations selecting one-dimensional policies. Individuals have single-peaked preferences, and they are impatient. Decisions arise from a bargaining game with random proposers and (super) majority approval, ranging from the simple majority up to unanimity. The existence and uniqueness of stationary subgame perfect equilibrium is established, and its explicit characterization provided. We supply an explicit formula to determine the unique alternative that prevails, as impatience vanishes, for each majority. As an application, we examine the efficiency of majority rules. For symmetric distributions of peaks unanimity is the unanimously preferred majority rule. For asymmetric populations rules maximizing social surplus are characterized.

Assesing advertising efficiency: does the internet play a role?

This research focuses on a major concern for marketers addressing the claims of inefficiency of the spending on advertising. We examine whether the Internet can help increase overall advertising efficiency. Using a sample from the Spanish automobile industry, we combine a nonparametric method - Data Envelopment Analysis - with recent important insights from statistics and econometrics studies, and we find that online advertising improves the efficiency levels and this effect is more pronounced in the long-term temporal framework.

The Design and efficiency of loyalty rewards

The goal of this paper is to reexamine the optimal design and efficiency of loyalty rewards in markets for final consumption goods. While the literature has emphasized the role of loyalty rewards as endogenous switching costs (which distort the efficient allocation of consumers), in this paper I analyze the ability of alternative designs to foster consumer participation and increase total surplus. First, the efficiency of loyalty rewards depend on their specific design. A commitment to the price of repeat purchases can involve substantial efficiency gains by reducing price-cost margins. However, discount policies imply higher future regular prices and are likely to reduce total surplus. Second, firms may prefer to set up inefficient rewards (discounts), especially in those circumstances where a commitment to the price of repeat purchases triggers Coasian dynamics.