Proton NMR Spectroscopy as a Probe of Dinuclear Copper(II) Active Sites in Metalloproteins. Characterization of the Hyperactive Copper(II)-Substituted Aminopeptidase from \u3cem\u3eAeromonas proteolytica\u3c/em\u3e

Proton NMR spectra of the hyperactive Cu(II)-substituted aminopeptidase from Aeromonas proteolytica (AAP) were recorded in both H2O and D2O buffered solution at pH 6.7. Several remarkably sharp, well resolved hyperfine shifted 1H NMR signals were observed in the 70 to −20 ppm chemical shift range. That hyperfine shifted signals were observed is due to spin-coupling of the two Cu(II) ions. Comparison of the spectra recorded in H2O and D2O buffered solutions indicated that the signals at 44.6, 43.3, and 17.7 ppm were solvent exchangeable. The two most strongly downfield shifted signals were assigned to imidazole N−H protons of the two coordinated histidine residues, while the remaining exchangeable signal was assigned to a peptidyl N−H proton that is in close proximity to the dicopper(II) center. One-dimensional NOE studies at pH 6.7 revealed two Y−CH2−CH\u3c moieties that were assigned to coordinated aspartic acid and histidine residues. In addition, a Y−CH2−CH2−CH\u3c moiety was also identified and was assigned to the coordinated glutamic acid residue, Glu152. All of the hyperfine shifted signals for [CuCu(AAP)] sharpened and shifted toward the diamagnetic region as the temperature was increased following Curie behavior. Fits of these data and those of a series of magnetically diverse μ-phenoxo and μ-alkoxo dicopper(II) model complexes to the population distribution of the ground and first excited states, provided information on the magnetic properties of dicopper(II) clusters. These fits indicated that the two Cu(II) ions in AAP are ferromagnetically coupled with a 2J value of 50 + 40 cm-1. These data provide the first structural information regarding the hyperactive [CuCu(AAP)] enzyme and are discussed in terms of the previously proposed mechanism of action for AAP

A Contractual Approach to Investor-State Regulatory Disputes

In 2010, Philip Morris International filed a complaint against Uruguay alleging that certain regulations on cigarette packaging violated the bilateral investment treaty (BIT) between Uruguay and the company\u27s home state of Switzerland. In its request for arbitration, Philip Morris claimed that the government\u27s anti-smoking legislation decreased the value of the company\u27s investments in the country in violation of Uruguay\u27s obligation under the BIT to provide fair and equitable treatment to Swiss investors. Among other things, the legislation requires that eighty percent of the surface area of cigarette packaging be devoted to health warnings, and that the packaging include graphic images ... to illustrate the adverse health effects of smoking. The arbitral tribunal in which the claim was filed recently determined that it had jurisdiction over at least some of Philip Morris\u27s claims, and the arbitration is now proceeding on the merits

Summary Dispositions as Precedent

The Supreme Court’s practice of summarily reversing decisions based on certiorari filings, without the benefit of merits briefing or oral argument, has recently come under increasing scrutiny. The practice is difficult to square with the Court’s stated criteria for granting certiorari and its norms against reviewing fact-bound cases to engage in mere error correction. Nonetheless, there is growing acceptance that the practice is likely to continue in some form, and the conversation has shifted to asking when the use of summary dispositions should be considered proper. Commentators have had no trouble identifying the Court’s tendencies: summary dispositions are most commonly used to rebuke the lower courts for attempting to resist Supreme Court doctrine, particularly in federal habeas and qualified immunity cases. But the Court’s failure to actually adopt this rationale creates legitimacy and rule-of-law concerns. Furthermore, it is unclear whether such rebuke is likely to be effective in achieving the Court’s apparent goal of harmonization. This Article proposes a novel, more constructive approach to summary dispositions that takes advantage of their unique attributes: they can be put to good use filling in the contours of general legal standards. It is well understood that standards acquire meaning only by application to a series of cases, but the Court does not have space on its plenary docket to take multiple cases in the same area to perform that function. Summary dispositions, including both affirmances and reversals, provide a mechanism for doing so in an efficient manner. This proposal is consistent with the standard criteria for granting certiorari, because the purpose would not be to correct the error in an individual case, but rather to provide more broadly useful precedential guidance about the meaning of the standard at issue. After describing this new purpose, the Article shows how existing practices should be revised to fulfill it more effectively. In particular, it develops a set of principled criteria for selecting cases to resolve by summary disposition, and calls for a more balanced approach that may be more effective in harmonizing lower-court decisions than the Court’s current emphasis on rebuking resistance

Suboptimal Human Rights Decision-Making

The literature on human rights generally assumes that when a state fails to comply with human rights norms, it is because the state’s leaders rationally determined that a violation would maximize the state’s expected utility. Strategies for improving compliance accordingly focus on altering a state’s expected utility calculation either through coercion, which seeks to introduce external incentives that make compliance more attractive, or persuasion, which seeks to recalibrate a state’s underlying preferences. A wide array of social science research, however, has demonstrated that human beings regularly make suboptimal decisions that fail to maximize their expected utility. This so-called behavioral research has had a significant impact on domestic law scholarship, but its implications for human rights, as well as for international law more broadly, have not yet been adequately explored. This Article begins that long-overdue conversation by showing that states may in some instances have an interest in complying with human rights norms but fail to do so as the result of suboptimal decision-making by their leaders. In particular, this Article explores how three strands of social science research—on prospect theory, overconfidence, and emotion-based decision-making—have been applied to state leaders in international relations scholarship and can be extended to help explain suboptimal decisions in the human rights context. In doing so, this Article also addresses (without attempting to conclusively resolve) some of the major methodological objections to such a project by collecting the most recent available research on the extent to which experimental findings about individuals in laboratories can be translated into predictions about state behavior. Two more detailed examples are then provided to illustrate how suboptimal decision-making may have contributed to human rights violations in real-world scenarios. Finally, this Article identifies several steps the human rights community can take, beyond coercion and persuasion, to capitalize on existing incentive structures and find ways to ensure that states that already have an interest in complying actually do so

A Contractual Approach to Investor-State Regulatory Disputes

International investment arbitral tribunals are increasingly tasked with resolving regulatory disputes. This relatively new form of dispute involves a challenge by a foreign investor to a host state’s generally applicable regulation, enacted in good faith to promote the public interest but resulting incidentally in harm to the investor’s business. Such claims typically invoke the “fair and equitable treatment” standard provided for in the bilateral investment treaty between the host state and the investor’s home state. The dominant view among commentators, and increasingly among the tribunals themselves, is that regulatory disputes should be analyzed within a public law framework, using tools derived from constitutional or administrative law. That means, for example, balancing the investor’s rights and host state’s regulatory concerns as part of a proportionality analysis. I argue that the public law approach is flawed because it requires tribunals to weigh incommensurable values and ultimately to make policy judgments when they lack the expertise and legitimacy to do so. This Article proposes that tribunals instead draw on tools from contract law and theory to approximate what the contracting states intended when they agreed to a fair and equitable treatment standard. The investment treaties themselves give no guidance on how that standard should be applied to regulatory disputes. When courts confront similar gaps in contracts, they do not simply abandon the inquiry into the parties’ intent but instead apply additional tools or principles to form the best possible estimate. The Article explores three specific tools: a default rule approach and two default standards derived from contract law’s analysis of changed circumstances. More generally, I argue that a contractual approach, by focusing tribunals on the contracting states’ intent rather than requiring them to independently assess the substance of a host state’s policy, will facilitate more principled reasoning as well as enhance the tribunals’ legitimacy, and thereby better promote the goals of international investment in the long run

Precedent and Dialogue in Investment Treaty Arbitration

Since the turn of the century, investment treaty arbitration (ITA) tribunals have begun citing past decisions with increasing frequency. They do so despite the absence of any formal doctrine of stare decisis and the presence of structural obstacles to the use of precedent in this context. Scholarship in this area has focused on explaining the rise of this de facto doctrine of precedent and evaluating the merits of the practice. Few have grappled with more practical questions about how precedent should operate in this unique sphere, but even a cursory examination of ITA decisions would reveal that some order and discipline are needed if the practice is to continue. This Article is the first to offer a comprehensive framework to guide ITA tribunals in the practice of precedent. It does so from the dual standpoints of interpreting precedent (how much deference is owed) and authoring precedent (how broadly or narrowly to write). The framework is designed to help tribunals at each stage balance the three key values of predictability, accuracy, and legitimacy that any system of precedent is expected to serve. And it shows how that balancing should be conducted in light of the distinctive institutional features that make ITA different from common law systems. At a high level, the proposal is to replace the common law approach of stable, incremental decisionmaking with a model of robust and contentious dialogue. That means tribunals should view past decisions skeptically and, in writing their own decisions, seek not just to resolve the immediate dispute at hand but to advance the broader conversation of which each case forms one part

Crafting Precedent

(with the Hon. Paul J. Watford & Marco Basile) How does the law of judicial precedent work in practice? That is the question at the heart of The Law of Judicial Precedent, a recent treatise by Bryan Garner and twelve distinguished appellate judges. The treatise sets aside more theoretical and familiar questions about whether and why earlier decisions (especially wrong ones) should bind courts in new cases. Instead, it offers an exhaustive how-to guide for practicing lawyers and judges: how to identify relevant precedents, how to weigh them, and how to interpret them. This Review takes up the treatise on its own terms as a practice guide for working lawyers and judges. Our initial aim is to identify how the treatise can be useful to lawyers and judges by describing its scope and drawing out some of its more salient lessons. Accordingly, in Part I, we provide a roadmap of the types of problems that the treatise addresses and the principles that it identifies for resolving them. Following the treatise, our discussion explores what types of precedents bind which courts and how much weight they should be given. In Part II, we home in on the distinct challenge of interpreting precedent. Although the treatise focuses on the reader’s task of interpreting an earlier decision, it also reveals how interpretation is really a “dialogue between courts.” That is, a future court ultimately decides what an earlier decision means, but the authoring court can facilitate that task by clarifying its decision’s reasoning and scope. We see this central insight as an opening to flip the treatise’s perspective and ask how the treatise’s insights on the interpretation of precedent can inform the writing of opinions that become precedents. Knowing the challenges future readers will face in reading and applying a case as precedent, what can the judge do at the front end of the process to craft more effective precedent? Part II is organized according to three key steps in the opinion-writing process: refining the question presented, identifying the governing law, and describing the material facts. At each step, we translate the guidance that the treatise provides for the interpretation process into lessons for authoring courts to consider at the drafting stage

Bilateral Investment Treaties and Domestic Institutional Reform

The bilateral investment treaties (BITs) signed between developed and developing countries are supposed to increase the flow of investment from the former to the latter. But the evidence indicates that the existing approach of guaranteeing special protections for foreign investors has only a modest impact on luring their dollars. At the same time they are failing to produce meaningful benefits, these treaty commitments create substantial costs for the host states that make them, exposing them to liability and constraining their regulatory authority. Given this state of imbalance, the time seems ripe for a new approach, but existing proposals for revising BITs are either insufficient or unrealistic, or in some instances even counterproductive. This Article calls for a fundamental redesign of BITs based on empirically validated premises about how host states actually attract foreign investment. Political science and economic studies show that foreign investors place substantial weight on the quality of domestic institutions. Existing BITs fail to promote investment because they are not an adequate substitute for these institutions, nor are they effective in generating reform. The proposed model would make domestic institutional reform the organizing principle of BIT design, and the Article offers several specific provisions that would help achieve that goal. Such an approach would produce immediate benefits for host states and so should be particularly attractive to developing countries. But the institutional reform model also retains the end goal shared by both sides of increasing foreign investment and so should be more realistically attainable than proposals pitched as benefiting developing states alone

Investigation of the transient fuel preburner manifold and combustor

A computational fluid dynamics (CFD) model with finite rate reactions, FDNS, was developed to study the start transient of the Space Shuttle Main Engine (SSME) fuel preburner (FPB). FDNS is a time accurate, pressure based CFD code. An upwind scheme was employed for spatial discretization. The upwind scheme was based on second and fourth order central differencing with adaptive artificial dissipation. A state of the art two-equation k-epsilon (T) turbulence model was employed for the turbulence calculation. A Pade' Rational Solution (PARASOL) chemistry algorithm was coupled with the point implicit procedure. FDNS was benchmarked with three well documented experiments: a confined swirling coaxial jet, a non-reactive ramjet dump combustor, and a reactive ramjet dump combustor. Excellent comparisons were obtained for the benchmark cases. The code was then used to study the start transient of an axisymmetric SSME fuel preburner. Predicted transient operation of the preburner agrees well with experiment. Furthermore, it was also found that an appreciable amount of unburned oxygen entered the turbine stages