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Objective To develop a usability checklist for public health dashboards. Materials and methods This study systematically evaluated all publicly available dashboards for sexually transmitted infections on state health department websites in the United States (N = 13). A set of 11 principles derived from the information visualization literature were used to identify usability problems that violate critical usability principles: spatial organization, information coding, consistency, removal of extraneous ink, recognition rather than recall, minimal action, dataset reduction, flexibility to user experience, understandability of contents, scientific integrity, and readability. Three user groups were considered for public health dashboards: public health practitioners, academic researchers, and the general public. Six reviewers with usability knowledge and diverse domain expertise examined the dashboards using a rubric based on the 11 principles. Data analysis included quantitative analysis of experts’ usability scores and qualitative synthesis of their textual comments. Results The dashboards had varying levels of complexity, and the usability scores were dependent on the dashboards’ complexity. Overall, understandability of contents, flexibility, and scientific integrity were the areas with the most major usability problems. The usability problems informed a checklist to improve performance in the 11 areas. Discussion The varying complexity of the dashboards suggests a diversity of target audiences. However, the identified usability problems suggest that dashboards’ effectiveness for different groups of users was limited. Conclusions The usability of public health data dashboards can be improved to accommodate different user groups. This checklist can guide the development of future public health dashboards to engage diverse audiences.

Palladium(0) nanoparticles have been widely used in cross coupling reactions, including Heck reactions. For this study, we synthesized palladium(0) nanoparticles in colloidal suspension using different combinations of solvents and reducing methods under aerobic conditions. The variation in systems used to synthesize palladium(0) nanoparticles resulted in different nanoparticle sizes. To investigate whether the particle size had an effect on catalysis, we first used common Heck C–C cross-coupling reaction conditions (200 °C and 18 h). In addition, we omitted the use of stabilizing agents, other than the solvent and/or the anions in the initial nanoparticle synthesis, since the use of stabilizing agents adds cost and processing time to catalysis. All of the catalysts investigated worked in the cross coupling C–C Heck reaction, but yields did not show appreciable differences, as high temperature and long reaction times promote a high reduction of palladium(II). Therefore, we decided to work with a temperature and reaction time in which conversion would start to be observed (minimum reaction conditions). The experiments to determine minimum reaction conditions showed that this would be 120 °C and 10 h, therefore we used these conditions in Heck C–C cross-coupling reactions and all the palladium nanoparticle systems. The best C–C catalysis conversion was observed when N,N-dimethylformamide was used as solvent in the absence of reducing agent. This catalyst system resulted in the largest possible nanoparticles, which were kept in dispersion (did not precipitate out), showing that size is important in obtaining good yields in C–C Heck catalysis (where cocktail-type catalysis could explain the conversion). Nanoparticles of this size also act as a reservoir of soluble palladium species that behave as the true catalyst. The second best conversion was observed in N,N-dimethylformamide with sodium citrate, where citrate may have added extra protection, and since the palladium(0) nanoparticles were small, cocktail-type catalysis was not involved in obtaining high yields.

Prior evidence suggests an association among food insecurity, poor health, and increased health care spending. In this study, we are using a natural experiment to confirm if longer participation in the Supplemental Nutrition Assistance Program (SNAP) is associated with reduced Medicaid spending among a highly impoverished group of adults. In 2013, the mandatory work requirements associated with SNAP benefits were lifted for able-bodied adults without dependents (ABAWDs). Using 2013 to 2015 Medicaid and SNAP data of 24,181 Minnesotans aged 18-49, we examined if changes in SNAP enrollment duration affect health care expenditures. In fully adjusted within-participant regression models, for each additional month of SNAP, average annual health care spending was $98.8 lower (95% CI: -131.7, -66.0; plt;.001) per person. Our data suggests that allowing ABAWDs to receive SNAP even in months they are not working may be critical to their health as well as cost-effective.

While investing in adolescents can foster growth and development opportunities, gender inequity and inadequate policy responses continue to undermine adolescent girls’ potential. The secondary effects of the COVID-19 pandemic exacerbate the health and development risks girls face. This article describes how the number of programs, policies, and studies targeting adolescent girls have increased in recent years, making higher quality evidence more available. However, systematic reviews of the evidence on intervention effectiveness often conclude with mixed results and implications. More research is needed on the under-explored dimensions of gender policies so policymakers can direct limited resources toward approaches proven to improve adolescent girls’ health, education, and wellbeing. Furthermore, ensuring the connection between evidence generation and evidence use remains an important—albeit unfinished—agenda, as demonstrated by case studies on evidence-informed policymaking for rural indigenous girls in Guatemala and girls at high risk of child marriage in Bangladesh. If adolescent girls are to thrive in tomorrow’s world, smarter investments are needed today to enable them to reach their full potential.

We report the study of a series of Ru-bipyridine (Ru-Bpy) complexes to correlate their photophysical and electrochemical properties to their performance in [4 + 2] cycloadditions, as a model reaction for electron transfer catalysis. Redox potentials, absorption and emission spectra, quantum yields and DFT calculations are presented to understand the catalytic transformation. The study shows that complex [Ru(Bpy) 3 ](PF 6 ) 2 is the more active photocatalyst, giving complete conversion to the product after 2 h reaction under white light. Any substitution in the para position of the Bpy ring decreases the reaction conversion. The [4 + 2] cycloaddition can be performed with different substrates and dienes, using either acetonitrile or nitromethane as solvents. Mechanistic studies suggest that the active catalyst for the transformation is [Ru(Bpy) 3 ] 3+ and that the rate determining step is the oxidation of [Ru(Bpy) 3 ] 2+ to generate the corresponding Ru 3+ species.

Although open government data (OGD) are becoming widely available, they have not yet reached their full potential due to their limited use. Supplementing OGD with visualizations can make data more engaging, useful, and understandable. We synthesized the academic research on the development and evaluation of OGD visualizations in the IEEE Explore, Science Direct, and ACM Digital Library databases. Our findings suggest four streams of research: 1) description and evaluation of specific examples of OGD visualization, 2) general tools and frameworks, 3) users' needs assessments and evaluation of usability, and 4) other user-related outcomes. While there is a growing robust literature describing specific cases, further empirical research is needed on evaluating the usability of OGD visualizations and tools for different audiences. Promising strategies to enhance the usability and usefulness of OGD are to employ advanced OGD platforms with embedded visualizations and analytics tools and to collaborate with research centers on user studies to ensure that visualizations and analytic tools are useful for stakeholders.

Palladium nanoparticles (PdNPs) prepared in neat glycerol containing TPPTS (tris(3-sulfophenyl)phosphine trisodium salt) or cinchona-based alkaloids (cinchonidine, quinidine) as capping agents, were applied as catalysts in fluoride-free Hiyama couplings and conjugate additions with the aim of evaluating the influence of the stabilizer in the catalytic reactivity. Therefore, PdNPs stabilized by phosphine favored C C cross-couplings, whereas those containing alkaloids showed enhanced suitability for C C homo-couplings and conjugate additions. The metal/stabilizer coordination mode, i.e. Pd P dative bond and π-π interaction between quinoline moiety and palladium surface, is certainly key for the stabilization of different active metallic species and then promoting distinctive catalytic pathways.

Thiolate-capped rhodium nanoparticles were synthesized by decomposition of the organometallic precursors [Rh(μ-SC12H25)(COD)]2 (I) and [Rh(μ-SC6H11)(COD)]2 (II) under hydrogen pressure, in imidazolium-based ionic liquids and organic solvent, without the external addition of ligands as stabilizers and were compared to RhNPs synthesized from [Rh(μ-OMe)(COD)]2. The use of ionic liquids during the synthesis of rhodium nanoparticles resulted in homogeneously well-dispersed systems as observed by TEM, where the thiolate ligand remains intact as demonstrated by XPS analysis and gas chromatography. The thiolate-capped rhodium nanoparticles generated from II were active catalysts in hydrogenation reactions with high selectivity towards alkene, nitro and imine groups. The absence of thiolate ligand generated very active catalytic systems and the hydrogenation of carbonyl groups was possible. The effect of thiol stabilizer was studied in the reductive N-alkylation to produce N-benzylaniline through one pot synthesis from benzaldehyde and nitrobenzene, where only the thiolate-capped RhNPs showed complete conversion and high selectivity. Additionally, the thiolate-capped RhNPs permitted the reuse of the catalytic systems for ten catalytic cycles for selected hydrogenation reactions after product separation.

Palladium nanoparticles (PdNPs) were synthesised and fully characterised, both in solution and the solid state, using naturally-occurring cinchona-based alkaloids in neat glycerol. These nano-systems were stable under reaction conditions, finding applications in hydrogenation and hydrodehalogenation processes, as a result of their surface-like behaviour. Their reactivity was improved in relation to that involving PdNPs stabilised by phosphines and also by Pd/C as a heterogenous catalyst, mainly in terms of recyclability. In particular, the colloidal palladium catalyst stabilised by quinidine was highly efficient to promote the hydrodechlorination of aromatic compounds under low dihydrogen pressure. These original catalysts found applications in the synthesis of secondary and tertiary amines including N-substituted anilines, by means of one-pot tandem Pd-catalysed methodologies under smooth conditions. In all of these processes, glycerol performed a crucial function as a liquid support for the immobilisation of nanoparticle-based catalysts, allowing both the stabilisation of the nano-catalysts and easy recycling of the catalytic phase.

article i nfo Palladium nanoparticles stabilized by thioether-phosphine ligands (1-3) were used as catalytic precursors in Heck-Mizoroki cross-coupling and C_C reduction reactions in ionic liquids. The ionic liquid (EMI)(MeHPO3) (A) exhibited an important hydrogen donor/acceptor behavior depending on the reaction conditions. Tandem or parallel pathways for C-C coupling and H-transfer reactions were observed, leading to the coupled product trans-4-phenyl-3-buten-2-one (I) and the corresponding reduced partner 4-phenylbutan-2-one (II) pointing toamolecular-likecatalyticreactivityoftheprocess.Whenthereactionwascarriedoutunderhydrogenpressure and low temperature, the reduction to II was inhibited by the presence of thioether-phosphine ligands.

In May 2013, per Congressional direction and to support a better understanding of pollution sources in the U. S. waters, the National Oceanic and Atmospheric Administration (NOAA) provided the U. S. Coast Guard (USCG) a detailed report on the assessment of risks from potentially polluting shipwrecks. The report, Risk Assessment for Potentially Polluting Wrecks in U.S. Waters, was a result of the Remediation of Underwater Legacy Environmental Threats (RULET) project that evaluated 20,000 shipwrecks for their pollution potential as well as issues that could impact operations including whether or not those wrecks could be historically significant properties and/or gravesites. “Historic property” is defined by the National Historic Preservation Act of 1966 (NHPA), to be any prehistoric or historic district, site, building, structure, or object included in, or eligible for inclusion in, the National Register of Historic Places (NRHP.) The NHPA requires a Federal agency to “take into account” the effects of its undertakings, such as pollution removal from a submerged shipwreck, and afford the Advisory Council on Historic Preservation (ACHP) a reasonable opportunity to comment. Federal agencies meet Section 106 responsibilities through a consultation process with the ACHP and other parties as set out in the ACHP's regulations implementing Section 106 of the NHPA (36 CFR Part 800), or through implementation of the nationwide 1997 Programmatic Agreement for emergency response under the National Oil and Hazardous Substances Pollution Contingency Plan. NOAA evaluated a number of the report's shipwrecks for eligibility under the NRHP criteria to determine if any could be considered historic properties. The majority of RULET sites are associated with World War II casualties in the Battle of the Atlantic. As of 2013, the average age of each wreck is 83 years old, as many were built or retrofitted for service during WWII, meeting one of the criteria, per the National Park Service's regulations at 36 CFR Part 60 for eligibility for nomination to the NRHP. Three potentially eligible shipwrecks were subsequently nominated and accepted to the NRHP. The information contained in the RULET risk assessments and the NRHP nominations, facilitates the efforts of USCG to work through the required consultation processes; more effectively balancing responsibilities to address potential environmental impacts and legal mandates to avoid or mitigate impacts to historic resources.

A Pd/(S)-BINAP system was successfully applied to the asymmetric allylic alkylation of rac-1,3-diphenyl-3-acetoxyprop-1-ene () using imidazolium-based ionic liquids (ILs) attaining up to 225 h(-1) TOF and 88% ee of the (R)-product. Although the system was barely active in the recycling experiments, the catalyst life was confirmed after recharging the system with substrate/reactants resulting in an alkylated product. In the latter case, the conversion rates and enantiomeric excesses were similar or lower compared to those in the first cycle. In order to explain the observed catalyst performance in the recycling as well as in the recharging experiments, we investigated the reactivity between the catalyst precursors, substrate and reactants in ILs. We were able to identify the species involved in the catalytic reactions under various conditions by means of (31)P NMR analyses. Allylpalladium intermediates () were found to be the active and selective species at a high substrate concentration. When the substrate was consumed, competing reactions took place leading to different palladium complexes. [PdCl(NHC(Bu,Me))((S)-BINAP)]Cl (), together with [Pd((S)-BINAP)2] (), were recognised as the species responsible for the loss of activity, meanwhile, the decrease in enantioselectivity was accounted for by the formation of mixed (NHC)(monophosphine)-palladium species.

Construction is under way at the Port of Long Beach’s middle harbor redevelopment project, combining two aging container terminals into one of the world’s most technologically advanced and most sustainable container shipping facilities. The project will double the capacity of the existing terminals and support 14,000 new jobs while cutting operational emissions in half. The first phase of the project went on-line at the end of 2015 with the full terminal build-out scheduled for 2020. In keeping with the port’s green port policy and the San Pedro Bay ports clean air action plan, the project was designed using principles of sustainable development to minimize or eliminate environmental and community impacts caused by shipping operations. Construction of this state-of-the-art terminal began in 2011 and will cost $1.314B when completed. This paper will discuss the environmental mitigation measures required to construct a state of the art terminal. Its influence on technologies implemented to maximize terminal efficiency and reduce emissions, and the infrastructure necessary to support such a terminal.

One of the most powerful approaches for the formation of simple and complex chiral molecules is the metal-catalysed asymmetric allylic alkylation. This reaction has been broadly studied with a great variety of substrates and nucleophiles under different reaction conditions and it has promoted the synthesis of new chiral ligands to be evaluated as asymmetric inductors. Although the mechanism as well as the active species equilibria are known, the performance of the catalytic system depends on the fine tuning of factors such as type of substrate, nucleophile nature, reaction medium, catalytic precursor and type of ligand used. Particularly interesting are chiral phosphines which have proved to be effective asymmetric inductors in several such reactions. The present review covers the application of phosphine-donor ligands in Pd-catalysed asymmetric allylic alkylation in the last decade.

We prepared new thioether-arylphosphines bearing alkyl and fluoroalkyl chains at the sulfur atom in order to use them in metal-catalyzed reactions in new reaction media, such as a fluorous biphasic system. The characterization of the new compounds is discussed and the partition coefficients in the biphasic system perfluoromethylcyclohexane-cyclohexane were determined. Fluorous thioether-phosphines reacted with [Rh(acac)(CO) 2 ] under fluorous biphasic conditions to produce rhodium species retained in the fluorous phase with

A new family of C2-symmetric chiral diphosphites was synthesized using two different chiral backbones derived from tartaric acid, combined with chiral binaphthyls or non-chiral substituted biphenyl moieties. Diphosphites were applied to Rh-catalyzed hydroformylation of styrene producing good conversions in mild conditions, fair regioselectivities but low enantioselectivities in all cases. Ligands were also essayed in Pd-catalyzed allylic substitution reactions of linear and cyclic substrates using dimethyl malonate as nucleophile. Conversion rates up to 7200 h−1 were reached, while moderated ee's were attained. In this reaction, a kinetic resolution of rac-1,3-diphenyl-3-acetoxyprop-1-ene was observed, leading to 99% ee of for the unreacted S-substrate and 60% ee of S-alkylated product. Coordination properties of diphosphites in rhodium and palladium complexes related to catalytic species involved in the two previous reactions were investigated. Some ligands form equatorial-equatorial chelates in pentacoordinated complexes [RhH(CO)(PPh3)(diphosphite)], while other act as bridge between two metal atoms. In the catalytic active species [Pd(η3-PhCHCHCHPh)(diphosphite)]PF6 one or two diastereoisomers are formed, depending on the diphosphite structure.

This review covers reports in the literature on the use of thioether ligands in Pd-catalysed asymmetric allylic substitution reactions from 1996 to June 2006. In the first section, we will cover the results using (S,S)-homo and (S,S)-heterodonor ligands. In the next section, we will present the results using heterodonor (S,X)-ligands, emphasizing the results obtained with (S,N)- and (S,P)-donor ligands. We also discuss any reported mechanistic aspects according to the allylic substitution results.

Responses to various types of mechanically induced wounding were followed in the giant-celled Caulerpalean species, Derbesia tenuissima, using time-lapse video-microscopy. Gametophyte vesicle cells. Puncture wounding: the gametophyte cell seals the puncture in 5 min. This is followed by cycles of ruptures and sealing, ending with full recovery in 24 hrs. Cut wounding: the protoplast immediately retracts away from the wall and reforms an intact, deflated protoplast that expands to fill the original cell within 21 hrs. Crush wounding (internal). When retained within the cell wall many protoplast fragments condense, round up, and coalesce; the reconstituted protoplast expands until it attains complete recovery, filling the original cell shape in 12 hrs. Crush wounding (external). Protoplast fragments extruded from the crushed cell are more numerous and smaller taking longer to recover. Most fragments become spherical, transforming into small viable cells capable of reproduction in several days. Sporophyte filaments. Crush wounding creates many small fragments that initially condense, coalesce and then expand within the wall to restore a complete filament with normal cytoplasmic streaming within 5 hrs. Reproduction: gametophyte. Our culture isolates produce more females than males (30:1). Gametangia develop one day before discharge that occurs explosively (1/6 sec) at first morning light. The vesicle cell forms successive gametangia every 14 days. Sporophyte. Each sporangium develops on a lateral branch that becomes isolated by the creation of successive basal plugs. After cytoplasmic cleavage and differentiation the stephanokont spores are discharged. The spores settle quickly and germinate forming gametophyte cells.

Palladium allylic systems containing modular chiral dithioether ligands were chosen as catalysts for a systematic study of homodonor ligands in allylic alkylation reactions. For this purpose, new t...

A series of cationic IrI complexes containing chiral dithioether ligands have been prepared in order to study the influence of the sulfur substituents and the metallacycle size on the acetamidoacrylate hydrogenation reaction. In the case of complexes 6, 7 and 10, a mixture of diastereomers is observed in solution due to the sulfur inversion processes. In contrast, this fluxional behaviour is efficiently controlled by using bicyclic ligands which inhibit the S-inversion in complexes 8 and 9. The solid-state structure of complex 10b shows only one diastereomer with the sulfur substituents in a relative anti disposition and in an overall configuration of SCSCSSSS at the coordinated dithioether ligand. Iridium complexes containing seven- and six-membered metallacycles (6b–d, 7b,c, 10a,b) react with the substrate through S-ligand substitution, and the rate of this substitution is related to the position of the fluorine atom on the aromatic ring. On the contrary, complexes containing a bismetallacycle (8 and 9) are not displaced by the substrate. The catalytic hydrogenation activity of complexes 8 and 9 is analysed in terms of the high stability of the corresponding dihydride complexes (13 and 14). In both cases, only two of the four possible diastereomeric dihydride species are formed in solution. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

This review covers the recent applications of chiral thioether ligands in asymmetric catalysis with transition metal complexes. S,S-Homo and S,X-heterodonor ligands are considered with special emphasis to their coordination chemistry. The results obtained with metal/thioether containing catalytic systems in asymmetric allylic substitution, hydrogenation, transfer hydrogenation, hydrosilylation, Michael addition, 1,4-conjugate addition and copolymerization reactions are reviewed including mechanistic considerations.

Arteriovenous graft (AVG) thrombosis is a frequent cause of graft failure. We evaluated coagulation protein concentrations, platelet function, and viscoelasticity factors in 20 hemodialysis (HD) patients with AVGs. The goal was to determine whether significant differences in protein concentrations, platelet function, and viscoelasticity factors exist among dialysis patients requiring frequent AVG declot procedures vs. those who do not. Twenty HD patients were enrolled: 10 frequent clotters (3 declots in the previous year) and 10 were nonclotters. Patients on antiplatelets or chronic anticoagulation were excluded. Laboratories were drawn pretreatment and heparinase was added to counteract any potential heparin effect. Coagulation protein concentrations including tissue factor (TF), thrombin/antithrombin III complex (TAT), and prothrombin fragment 1 + 2 (F(1+2)) were assayed. The time to clot onset was measured by force onset time (FOT). Platelet contractile force (PCF) measured the force produced by platelets during clot retraction, whereas clot rigidity was measured as clot elastic modulus (CEM). FOT, CEM, and PCF were measured by Hemodyne. Both groups had upregulation of the TF pathway, as TF, TAT, and F(1+2) levels were similarly increased over baseline levels. Hemodialysis patients with frequent AVG clotting had higher levels of both PCF and CEM compared with nonclotters. Additionally, the frequent clotters had a lower FOT relative to nonclotters, although both were considered in the normal range. Our study suggests that HD patients with recurrent AVG thrombotic events form clots with higher tensile strength compared with HD patients without recurrent graft thrombosis.

Thioether-phosphines, 1 and 2, were applied for the stabilisation of palladium nanoparticles (PdNPs) synthesised by a bottom-up methodology, using [Pd2(dba)3] as an organometallic precursor. For the phenyl containing ligand 1, small (d(mean) = 1.6 nm), well-defined and dispersed nanoparticles were obtained; however, ligand 2 involving a long alkyl chain led to agglomerates. NMR and GC-MS analyses throughout the synthesis of the nanomaterials revealed partial cleavage of ligands by C-S and C-P bond activations, and XPS spectra of the isolated nanoparticles indicated the presence of both thioether-phosphines and their fragments on the metallic surface. Reactivity studies of molecular palladium systems as well as on extended palladium surfaces pointed out that cluster entities are responsible for C-heteroatom activations, triggering structure modifications of stabilisers during the synthesis of PdNPs.

The synthesis of a new family of systematically modified chiral dithioethers to be used as ligands is described. Phenylthioether derivative 5 and fluorine-containing dithioether ligands 6 – 8 and 13 – 15 were prepared by direct reaction of phenylthiol and o -, m - or p -fluorophenylthiol with two different ditriflate derivatives based on the l -tartaric skeleton. The chiral ditriflate 12 containing a dioxolane moiety was reacted with ethane- and propanedithiol, producing cyclic dithioethers 16 and 17 , respectively, in good yields (≈50%). The analogous ditriflate 4 with benzyl ether protecting groups, having a skeleton without restricted rotation, gave the thiolane 9 as the main product.

The Robinson House site is situated within the Manassas National Battlefield Park in northern Virginia. The original Robinson House was constructed in the 1840s and was occupied until 1936 by the same free African-American family. The National Park Service recognizes and interprets the Robinson House since it was part of the Civil War battlefield landscape during the First and Second Battles of Manassas. The original house went through a series of structural additions and alterations in the late 1800s and early 1900s. The house stood until 1993 when arsonists burned it, causing 60% damage to the structure. Today, the east chimney and the stone foundations remain. Amidst the many Civil War monuments at the battlefield park the interpretation of a century of occupation by the Robinson family through the remaining foundations adds meaning and depth to the area's local history. The Robinson House remains symbolize an African-American family's way of life as well as their struggle to survive during Reconstruction and the Jim Crow era. The foundations and site are a steadfast symbol of African-American cultural persistence that has prevailed for over 100 years on a battlefield landscape.

Historically, health care spending has not been very sensitive to short-term economic disruptions. However, data show some notable changes in health care spending and utilization since the recession of 2007-2008 both nationally and in Minnesota. This article presents trends emerging from that data and discusses potential reasons for them. It also highlights other factors such as structural changes in health care delivery that were occurring before, during, and after the economic downturn, that might account for the trends.

New catalytic systems based on in situ and preformed palladium nanoparticles in ionic liquids (characterised by TEM) starting from palladium acetate or dipalladiumtris(dibenzylideneacetone) have been applied in the synthesis of 4-phenylbutan-2-one (II), a model compound for the preparation of fragrances. Imidazolium-based ionic liquid containing a methyl hydrogenophosphonate anion leads to an efficient Pd-catalyzed tandem coupling/reduction process, taking advantage of the multi-role of this solvent (nanoparticles stabiliser, base, hydrogen transfer agent). The influence of the mono-phosphine ligands (1-3) on the catalyst has been evaluated, showing that the ligand-free palladium system turns into the most appropriate for the formation of II using Pd(OAc)(2) as precursor. Fine-tuning conditions involved in this multi-parameter process have led us to propose a plausible mechanism based on the hydrogen transfer coming from the methyl hydrogenophosphonate anion.

By reacting [Pt(SR)2COD] with K2[Pt(SR′)4] (R and R′C6F5 or p-C6HF4) platinum(II) homoleptic binuclear compounds with bridging fluorothiolate groups are obtained. Compounds bearing mixed ligands show a variety of isomers in solution.

This review covers reports in the literature on the use of thioether ligands in Pd-catalysed asymmetric allylic substitution reactions from 1996 to June 2006. In the first section, we will cover the results using (S,S)-homo and (S,S)-heterodonor ligands. In the next section, we will present the results using heterodonor (S,X)-ligands, emphasizing the results obtained with (S,N)- and (S,P)-donor ligands. We also discuss any reported mechanistic aspects according to the allylic substitution results.

The preparation and characterization of the new thiolate complexes [M(SR)2(SEt2)2] (M=Pt, R=C6F5 orp-C6HF4) and [M(SR)2]n (M=Pd, R=C6F5,p-C6HF4 orp-C6H4F; M=Pt, R=p-C6H4F) is discussed. The tendency to form polymeric, rather than monomeric species, varies as follows: Pd>Pt; C6H4F>C6HF4> C6F5. [Pt(SC6F5)2(SEt2)2] has atrans square planar coordination.

P-selectin, a member of the selectin family, is a vascular cell adhesion molecule. It is expressed and stored in alpha granules of platelets and in Weibel-Palade bodies of endothelial cells, and upon activation, P-selectin is translocated/transferred to the membrane surface. A key function of the P-selectin is to mediate leukocyte, lymphocyte and platelet interactions in inflammation and possibly in the thrombus formation. A soluble variant, S-Psel, comprising the extracellular domain of P-selectin, has been identified in healthy individuals, but is markedly elevated in patient with vascular disorders. Recent work on S-Psel suggested that S-Psel may play a role in hemostasis/coagulation through the generation of procoagulant TF-bearing microparticles (MP), and therefore, has potential in treating patients with the bleeding disorders, like hemophilia. The aim of this study is to verify studies reporting that S-Psel exhibits in vitro and in vivo pro-coagulant activity. S-Psel and S-Psel-Fc (IgG) fusion were purchased commercially or prepared at Novo Nordisk Research US (NNRUS) and their biological activity was verified by P-selectin/Pselectin glycoprotein ligand-1(PSGL-1) interaction in vitro. The clotting times of human whole blood and plasma treated with S-Psel or S-Psel-Fc, or with an irrelevant human IgG control protein, were measured by thromboelastography and aggregometry respectively. After up to 8 hours of incubation with S-Psel and S-Psel-Fc at a concentration of 15ug/ml, we found no significant difference between samples treated with S-Psel, S-Psel-Fc and the IgG controls. The ability of S-Psel to generate TF-bearing microparticles in human whole blood was examined in a FXa substrate cleavage assay; however, no significant difference in cleavage was observed. Finally, we evaluated S-Psel in vivo. Hemophilia A mice were injected with recombinant mouse S-Psel-IgG or S-Psel-Fc (IgG) at the concentration of 1.2 mg/Kg body weight and human IgG was used as control. As suggested from published results, the effect of S-Psel was determined 6 h after the treatment. Contrary to previous reports, the results revealed no significant difference in bleed time and blood loss between the experimental and control group. In conclusion, we were unable to demonstrate the procoagulant activity of S-Psel in our laboratory either in vitro or in vivo.

Chiral dithioether ligands have been tested in the model Pd-catalysed allylic alkylation reaction of (±)-3-acetoxy-1,3-diphenyl-1-propene with dimethyl malonate, giving high enantioselectivity (up to 81% e.e.) for the first time in this type of system. Pd(II)-allylic intermediates, [Pd(η3-1,3-Ph2-C3H3)(dithioether)]PF6 were prepared and characterised both in solution by NMR spectroscopy and solid state. The X-ray structure for [Pd(η3-1,3-Ph2-C3H3)(L)]PF6 (L=(R,R)-7,8-O-isopropylidene-1,5-dithia-cyclononane) was determined.

The syntheses of the persulfurated [M(SRF)2(CH3SCH(CH3)CH(CH3)SCH3)], M=Pd or Pt; RF=C6F5 or C6F4H-4 compounds allow the separation of two diastereomers and the NMR detection of five conformers (three anti and two syn) of each compound. 1H, 19F and 195Pt NMR data have been used to assign each conformer and to obtain their relative populations as well as to follow their equilibrium at high temperatures. The X-ray diffraction molecular and crystalline structure of [Pt(SC6F5)2(CH3SCH(CH3)CH(CH3)SCH3)] has been determined.