Insight into the unexpectedly small range of isotropic nitrogen chemical shifts in nitrobenzene derivatives is gained through measurements of the chemical shift (CS) tensor by solid-state NMR experiments and ab initio molecular orbital (MO) and density functional theory (DFT) calculations. The principal components, delta(ii), of the (15)N CS tensors have been measured for nitrobenzene, 4-nitroaniline, 4-nitrotoluene, 4-nitroanisole, 4-nitroacetophenone, nitromesitylene, and 2,4,6-tri-tert-butylnitrobenzene. No obvious correlations of the delta(ii) values with traditional reactivity parameters were observed. The CS tensor components change significantly for the para-substituted nitrobenzenes, but these variations nearly cancel to yield isotropic shifts that fall in a range of only 3 ppm. Ab initio calculations of the delta(ii) values at the HF level are in poor agreement with the experimental values, whereas MP2 calculations and DFT calculations employing the B3LYP functional are in better agreement with experiment. The calculated (B3LYP/6-311G) delta(ii) values follow a trend in which delta(11) and delta(33) increase while delta(22) decreases with the accepted electron withdrawing ability of the para substituent. These changes tend to cancel yielding a variation in delta(iso) of only 4 ppm. These calculations indicate that the CS tensor has the same orientation as the carbon CS tensor in the isoelectronic benzoate anion: delta(11) bisects the O-N-O angle, delta(33) is perpendicular to the NO(2) plane, and delta(22) is in the NO(2) plane and perpendicular to delta(11).
Solvency II is currently one of the most sophisticated insurance regulatory regimes in the world. It is built around the principles of market consistency and embedding strong risk management and governance within insurance companies. For business with long-term guarantees, the original basis produced outcomes that were unacceptable to the member states. The original design was amended through Omnibus II. The working party has looked back at the outcome of the final regulation and comments on how well Solvency II has fared, principally from a UK perspective, relative to its initial goals of improved consumer protection, harmonisation, effective risk management and financial stability. We review Pillar 1's market consistent valuation (including the risk margin and transitional measures) as well as the capital requirements (including internal models). We look at the impact this has on asset and liability management, pro-cyclicality and product design. We look at Pillars 2 and 3 in respect of the Own Risk and Solvency Assessment, liquidity and disclosure. Finally, we stand back and look at harmonisation and the implications of Brexit. In summary we conclude that Solvency II represents a huge improvement over Solvency I although it has not fully achieved the goals it aspired to. There are acknowledged shortfalls and imperfections where adjustments to Solvency II are likely. There remain other concerns around pro-cyclicality, and the appropriateness of market consistency is still open to criticism. It is hoped that the paper and the discussion that goes with it provide an insight into where Solvency II has taken European Insurance regulation and the directions in which it could evolve. KeywordsSolvency II; Market consistency; Effective risk management; Risk margin; Brexit 1. Summary of Paper and Conclusions of the Working Party 1.1. Solvency II Solvency II has been under consideration and development since the early 2000s. The previous regime, in force since the 1970s (which had come to be known as Solvency I), was not risk-sensitive and a number of key risks, including market, credit and operational risks, were not explicitly taken into account in capital requirements. Furthermore, Solvency I permitted the continuation of different methodologies in different EU countries, e.g., either book or market value of either assets or liabilities, depending on country.
Prior-authorization requirements and copayments for medications may present barriers to refilling medications for Medicaid beneficiaries with schizophrenia or bipolar disorder. State Medicaid programs should consider the unintended consequences of medication utilization management practices for this population.
Medicaid beneficiaries with schizophrenia and bipolar disorder require a range of services and supports. This descriptive study used 2007 Medicaid claims data from 21 states and the District of Columbia to examine the extent to which this population received guideline-concordant medications, medication monitoring, outpatient mental health care, and preventive physical health care. More than 80 % of beneficiaries in each state filled at least one prescription for a guideline-concordant medication during the year but, on average, only 57 % of those with schizophrenia and 45 % of those with bipolar disorder maintained a continuous supply of medications. Roughly 25 % did not have an outpatient mental health visit during the year (excluding case management and some other services); in some states more than half did not have such a visit. Only 11 % of beneficiaries received a physical health examination or health behavior counseling when claims codes were used to identify these services rather than all primary care physician visits. Less than 5 % of beneficiaries maintained their supply of medications, received medication monitoring and had an outpatient mental health visit, physical health examination or received health behavior counseling during the year. Although these rates of service utilization are likely conservative and the data predate recent efforts to integrate care, the findings underscore the need for quality improvement efforts targeted to this population and may provide a baseline for monitoring progress.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.