Direct Observation of High-Spin States in Manganese Dimer and Trimer Cations by X-ray Magnetic Circular Dichroism Spectroscopy in an Ion Trap

The electronic structure and magnetic moments of free Mn$_2^+$ and Mn$_3^+$ are characterized by $2p$ x-ray absorption and x-ray magnetic circular dichroism spectroscopy in a cryogenic ion trap that is coupled to a synchrotron radiation beamline. Our results show directly that localized magnetic moments of 5 $\mu_B$ are created by $3d^5 (^6\mathrm{S})$ states at each ionic core, which are coupled in parallel to form molecular high-spin states via indirect exchange that is mediated in both cases by a delocalized valence electron in a singly-occupied $4s$ derived orbital with an unpaired spin. This leads to total magnetic moments of 11 $\mu_B$ for Mn$_2^+$ and 16 $\mu_B$ for Mn$_3^+$, with no contribution of orbital angular momentum

Predicting Secondary Structures, Contact Numbers, and Residue-wise Contact Orders of Native Protein Structure from Amino Acid Sequence by Critical Random Networks

Prediction of one-dimensional protein structures such as secondary structures and contact numbers is useful for the three-dimensional structure prediction and important for the understanding of sequence-structure relationship. Here we present a new machine-learning method, critical random networks (CRNs), for predicting one-dimensional structures, and apply it, with position-specific scoring matrices, to the prediction of secondary structures (SS), contact numbers (CN), and residue-wise contact orders (RWCO). The present method achieves, on average, $Q_3$ accuracy of 77.8% for SS, correlation coefficients of 0.726 and 0.601 for CN and RWCO, respectively. The accuracy of the SS prediction is comparable to other state-of-the-art methods, and that of the CN prediction is a significant improvement over previous methods. We give a detailed formulation of critical random networks-based prediction scheme, and examine the context-dependence of prediction accuracies. In order to study the nonlinear and multi-body effects, we compare the CRNs-based method with a purely linear method based on position-specific scoring matrices. Although not superior to the CRNs-based method, the surprisingly good accuracy achieved by the linear method highlights the difficulty in extracting structural features of higher order from amino acid sequence beyond that provided by the position-specific scoring matrices.Comment: 20 pages, 1 figure, 5 tables; minor revision; accepted for publication in BIOPHYSIC

Characterization of on-road vehicle emissions in the Mexico City Metropolitan Area using a mobile laboratory in chase and fleet average measurement modes during the MCMA-2003 field campaign

A mobile laboratory was used to measure on-road vehicle emission ratios during the MCMA-2003 field campaign held during the spring of 2003 in the Mexico City Metropolitan Area (MCMA). The measured emission ratios represent a sample of emissions of in-use vehicles under real world driving conditions for the MCMA. From the relative amounts of NO_x and selected VOC's sampled, the results indicate that the technique is capable of differentiating among vehicle categories and fuel type in real world driving conditions. Emission ratios for NO_x, NO_y, NH₃, H₂CO, CH₃CHO, and other selected volatile organic compounds (VOCs) are presented for chase sampled vehicles in the form of frequency distributions as well as estimates for the fleet averaged emissions. Our measurements of emission ratios for both CNG and gasoline powered "colectivos" (public transportation buses that are intensively used in the MCMA) indicate that – in a mole per mole basis – have significantly larger NO_x and aldehydes emissions ratios as compared to other sampled vehicles in the MCMA. Similarly, ratios of selected VOCs and NO_y showed a strong dependence on traffic mode. These results are compared with the vehicle emissions inventory for the MCMA, other vehicle emissions measurements in the MCMA, and measurements of on-road emissions in U.S. cities. We estimate NO_x emissions as 100 600±29 200 metric tons per year for light duty gasoline vehicles in the MCMA for 2003. According to these results, annual NO_x emissions estimated in the emissions inventory for this category are within the range of our estimated NO_x annual emissions. Our estimates for motor vehicle emissions of benzene, toluene, formaldehyde, and acetaldehyde in the MCMA indicate these species are present in concentrations higher than previously reported. The high motor vehicle aldehyde emissions may have an impact on the photochemistry of urban areas

Meta‐analysis of oral antibiotics, in combination with preoperative intravenous antibiotics and mechanical bowel preparation the day before surgery, compared with intravenous antibiotics and mechanical bowel preparation alone to reduce surgical‐site infections in elective colorectal surgery

Background: Surgical‐site infection (SSI) is a potentially serious complication following colorectal surgery. The present systematic review and meta‐analysis aimed to investigate the effect of preoperative oral antibiotics and mechanical bowel preparation (MBP) on SSI rates. Methods: A systematic review of PubMed, Cochrane Database of Systematic Reviews and Cochrane Central Register of Controlled Trials was performed using appropriate keywords. Included were RCTs and observational studies reporting rates of SSI following elective colorectal surgery, in patients given preoperative oral antibiotic prophylaxis, in combination with intravenous (i.v.) antibiotic prophylaxis and MBP, compared with patients given only i.v. antibiotic prophylaxis with MBP. A meta‐analysis was undertaken. Results: Twenty‐two studies (57 207 patients) were included, of which 14 were RCTs and eight observational studies. Preoperative oral antibiotics, in combination with i.v. antibiotics and MBP, were associated with significantly lower rates of SSI than combined i.v. antibiotics and MBP in RCTs (odds ratio (OR) 0·45, 95 per cent c.i. 0·34 to 0·59; P < 0·001) and cohort studies (OR 0·47, 0·44 to 0·50; P < 0·001). There was a similarly significant effect on SSI with use of a combination of preoperative oral aminoglycoside and erythromycin (OR 0·40, 0·25 to 0·64; P < 0·001), or preoperative oral aminoglycoside and metronidazole (OR 0·51, 0·39 to 0·68; P < 0·001). Preoperative oral antibiotics were significantly associated with reduced postoperative rates of anastomotic leak, ileus, reoperation, readmission and mortality in the cohort studies. Conclusion: Oral antibiotic prophylaxis, in combination with MBP and i.v. antibiotics, is superior to MBP and i.v. antibiotic prophylaxis alone in reducing SSI in elective colorectal surgery

Chaos in cosmological Hamiltonians

This paper summarises a numerical investigation which aimed to identify and characterise regular and chaotic behaviour in time-dependent Hamiltonians H(r,p,t) = p^2/2 + U(r,t), with U=R(t)V(r) or U=V[R(t)r], where V(r) is a polynomial in x, y, and/or z, and R = const * t^p is a time-dependent scale factor. When p is not too negative, one can distinguish between regular and chaotic behaviour by determining whether an orbit segment exhibits a sensitive dependence on initial conditions. However, chaotic segments in these potentials differ from chaotic segments in time-independent potentials in that a small initial perturbation will usually exhibit a sub- or super-exponential growth in time. Although not periodic, regular segments typically exhibit simpler shapes, topologies, and Fourier spectra than do chaotic segments. This distinction between regular and chaotic behaviour is not absolute since a single orbit segment can seemingly change from regular to chaotic and visa versa. All these observed phenomena can be understood in terms of a simple theoretical model.Comment: 16 pages LaTeX, including 5 figures, no macros require

Competing for Refugees: A Market-Based Solution to a Humanitarian Crisis

The current refugee crisis demands novel legal solutions, and new ways of summoning the political will to implement them. As a matter of national incentives, the goal must be to design mechanisms that discourage countries of origin from creating refugees, and encourage host countries to welcome them. One way to achieve this would be to recognize that persecuted refugee groups have a financial claim against their countries of origin, and that this claim can be traded to host nations in exchange for acceptance. Modifications to the international apparatus would be necessary, but the basic legal elements of this proposal already exist. In short, international law can and should give refugees a legal asset, give host nations incentives to accept them, and give oppressive countries of origin the bill

Salt intrusion in multi-channel estuaries: a case study in the Mekong Delta, Vietnam

There is a well-tested theory for the computation of salt intrusion in alluvial estuaries that is fully analytical and predictive. The theory uses analytical equations to predict the mixing behaviour of the estuary based on measurable quantities, such as channel topography, river discharge and tidal characteristics. It applies to single-channel topographies and estuaries that demonstrate moderate tidal damping. The Mekong delta is a multi-channel estuary where the tide is damped due to a relatively strong river discharge (in the order of 2000 m³/s), even during the dry season. As a result the Mekong is a strongly riverine estuary. This paper aims to test if the theory can be applied to such a riverine multi-channel estuary, and to see if possible adjustments or generalisations need to be made. The paper presents salt intrusion measurements that were done by moving boat in 2005, to which the salt intrusion model was calibrated. The theory has been expanded to cater for tidal damping. Subsequently the model has been validated with observations made at fixed locations over the years 1998 and 1999. Finally it has been tested whether the Mekong calibration fits the overall predictive equations derived in other estuaries. The test has been successful and led to a slight adjustment of the predictive equation to cater for estuaries that experience a sloping bottom

Fairness, Efficiency and Insider Trading: Deconstructing the Coin of the Realm in the Information Age

Whether and how the federal securities laws should restrict insider trading is one of the most hotly debated topics in the securities law literature. Paradoxically, both the theoretical analysis and the legal rules concerning insider trading remain extraordinarily vague and ill-formed. What is the special character of insider trading that leads to this apparently irresolvable puzzle? In this Article, I argue that there is, in fact, nothing special about insider trading that creates this dilemma, but rather there is something special about the nature of information itself. Accordingly, this theoretical dilemma is not limited to insider trading regulation, but rather pervades all areas of intellectual property law. In this Article, I situate insider trading regulation within the larger body of intellectual property law by discussing three potential allocations of the property right in valuable inside information. First, inside information could be treated as a public resource, meaning that a person in possession of inside information could not legally exploit that advantage for personal profit. Such a regime would forbid some or all insider trading by forcing the disclosure to the marketplace of inside information prior to trading. I argue that regulators should reject this alternative because, despite it\u27s proponents\u27 tendency to justify the rule in terms of fairness, this proposal is unlikely to foster fairness in any meaningful way. Alternatively, the property right in valuable inside information could belong to issuers, as the producers of such information. I argue that regulators should reject this alternative because, despite its proponents? tendency to frame their arguments in terms of promoting informational efficiency, a legal regime treating inside information as the property of the issuer is unlikely to further that goal. In fact, such proposals assume an affirmative answer to a question that is fiercely debated in other areas of intellectual property law: does creating a property right in information producers incentivize additional production to the extent necessary to offset the social costs of excluding others from use of the information? Finally, the property right in valuable inside information could reside with outsider traders (traders who possess inside information, but are neither insiders nor constructive insiders of the issuer). I argue that regulators should pursue this alternative because, although there is no need to encourage issuers to create valuable inside information, the need to encourage the dissemination of such information to the marketplace has been recognized for many years. Accordingly, I propose in this Article a system of federal securities regulation that would permit trading by corporate outsiders who did not receive their information in a tip from an insider or constructive insider. Such a system, I argue, provides the hope of filling in the gaps left by the current disclose or abstain system, by encouraging the reflection of material information in stock market price without disclosure of the actual inside information. At the same time, this proposal avoids the perverse incentives and negative impacts on market efficiency attendant in a system that permits insider trading by corporate employees

Go with your gut! Effects of affect misattribution procedures become stronger when participants are encouraged to rely on their gut feelings

The Affective Misattribution Procedure (AMP) is one of the leading examples of a class of tasks used to measure attitudes implicitly. Based on the idea that AMP effects occur because participants misattribute affective responses, we hypothesized that asking participants to focus on their affective, gut-level responses would increase the magnitude of AMP effects. In line with this prediction, results showed that participants who completed the AMP while "going with their gut" revealed AMP effects that were much larger than for participants who completed the AMP with standard instructions. This result supports the prevailing model of the AMP as being related to affective misattribution, and reveals a straightforward way to increase effect sizes in the AMP