A series of dicationic bis-chelated palladium(II) complexes [Pd(N-N)2][X]2 (N-N = 2,2‘-bipyridine (bipy), 1,10-phenanthroline (phen), and their substituted derivatives; X = PF6 -, BF4 -, OTf-, OTs-) has been synthesized and completely characterized both in the solid state and in solution. The synthetic procedure involves a simple one-pot reaction between Pd(MeCOO)2 and [(N-N)H][X]. These compounds are very active precatalysts for the CO/styrene copolymerization yielding perfectly alternating polyketones. The crystal structures of some complexes of the series provide evidence that a distorsion from the ideal square planar geometry toward a twist conformation occurs. In DMSO solution, one of the two nitrogen-donor ligands is involved in a dissociative equilibrium yielding a monochelated complex with two cis coordination sites available for the copolymerization catalytic process. The catalytically active species is very stable in 2,2,2-trifluoroethanol, where its activity was found unaltered for at least 48 h of reaction without apparent decomposition to palladium metal. The addition of 1,4-benzoquinone (BQ) to the catalytic system has a strong influence on the yield and, above all, on the molecular weight of polyketones. The zerovalent palladium complexes [Pd(N-N)(BQ)], which might be formed during the copolymerization process, have been synthesized and characterized. The crystal structure of [Pd(bipy)(BQ)] shows that benzoquinone acts as a mono-olefinic ligand to Pd. In the presence of protons, the Pd(0) complexes are readily oxidized to Pd(II) with the reduction of benzoquinone to hydroquinone. When [(N-N)H][X] is used as the source of protons, the resulting Pd(II) species is the precatalyst and can immediately re-enter the catalytic cycle.

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The objective of this study was to propose a rough but simple method for estimating the total population need for opioids for treating all various types of moderate and severe pain at the country, regional, and global levels. We determined per capita need of strong opioids for pain related to three important pain causes for 188 countries. These needs were extrapolated to the needs for all the various types of pain by using an adequacy level derived from the top 20 countries in the Human Development Index. By comparing with the actual consumption levels for relevant strong opioid analgesics, we were able to estimate the level of adequacy of opioid consumption for each country. Good access to pain management is rather the exception than the rule: 5.5 billion people (83% of the world's population) live in countries with low to nonexistent access, 250 million (4%) have moderate access, and only 460 million people (7%) have adequate access. Insufficient data are available for 430 million (7%). The consumption of opioid analgesics is inadequate to provide sufficient pain relief around the world. Only the populations of some industrialized countries have good access. Policies should seek a balance between maximizing access for medical use and minimizing abuse and dependence. Countries should aim to increase the medical consumption to the magnitude needed to address the totality of moderate and severe pain.

A new nonsymmetric bis(aryl‐imino)acenaphthene (Ar‐BIAN) ligand, featured by a subtle steric and electronic unbalance of the N‐donor atoms, is reported. With the new ligand and the corresponding symmetrically substituted derivatives, both neutral and monocationic PdCH3 compounds have been synthesized and characterized. The series of the monocationic complexes [Pd(CH3)(L)(Ar‐BIAN)][PF6] (L=CH3CN, dmso) has been extended to dimethyl sulfoxide derivatives. The monocationic complexes are tested as precatalysts for the ethylene/methyl acrylate cooligomerization under mild reaction conditions of temperature and ethylene pressure. The catalytic product is a mixture of ethylene/acrylate cooligomers and higher alkenes. The catalysts containing the new nonsymmetric ligand are found to be more productive than those with the symmetric Ar‐BIANs. The Pd–dmso catalysts are more productive and show a longer lifetime than their Pd–NCCH3 counterparts.

Introduction:Leishmaniasis is a parasitic disease transmitted by phlebotomine sandflies. Between 700,000 and 1.2 million cases of cutaneous leishmaniasis and between 200,000 and 400,000 cases of visceral leishmaniasis (VL), which is fatal if left untreated, occur annually worldwide. Liposomal amphotericin B (LAMB), alone or in combination with other drugs, has been extensively studied as VL treatment, but data on routine field use are limited, and several challenges to patients' access to this life-saving drug remain.Areas covered:This article provides a review of clinical studies on LAMB for VL and other forms of leishmaniasis. The current development of generic versions of LAMB and related challenges are also discussed.Expert opinion:LAMB proved to be highly efficacious and safe in over 8000 VL patients treated by MÉdecins Sans Frontières in South Asia, and its use was feasible even at primary healthcare level. Despite requiring higher doses, LAMB is the drug of choice to treat vulnerable groups (e.g., pregnant or HIV positive) and relapsing VL patients in East Africa. LAMB should be included in national VL guidelines and registered in all VL endemic countries. Its cost should be further reduced and regulatory pathways to prove bioequivalence for generic LAMB products should be implemented.