In Search for Titanocene Complexes with Improved Cytotoxic Activity: Synthesis, X-Ray Structure, and Spectroscopic Study of Bis(η5-cyclopentadienyl)difluorotitanium(IV)

The 1 : 2 reaction of [Ti(η5-C5H5)2Cl2] and AgF in CHCl3/H2O yielded the fluoro analog [Ti(η5-C5H5)2F2] (1) in almost quantitative yield (C5H5 is the cyclopentadienyl group). The coordination about the TiIV atom formed by two fluoro ligands and the centroids of the cyclopentadienyl rings is distorted tetrahedral. The compound crystallizes in the orthorhombic space group C2cm. The lattice constants are a = 5.9055(4), b = 10.3021(5), c = 14.2619(9) Å, and α = β = γ = 90°. The complex has been characterized by elemental analyses and spectroscopic (IR, 1H NMR) data. A structural comparison of the four members of the [Ti(η5-C5H5)2X2] family of complexes (X = F, Cl, Br, I) is attempted

Use of the 2-Pyridinealdoxime/N,N′-Donor Ligand Combination in Cobalt(III) Chemistry: Synthesis and Characterization of Two Cationic Mononuclear Cobalt(III) Complexes

The use of 2-pyridinealdoxime (paoH)/N,N′-donor ligand (L-L) “blend” in cobalt chemistry has afforded two cationic mononuclear cobalt(III) complexes of the general type [Co(pao)2(L-L)]+, where L-L = 1,10-phenanthroline (phen) and 2,2′-bipyridine (bpy). The CoCl2/paoH/L-L (1 : 2 : 1) reaction system in MeOH gives complexes [CoIII(pao)2(phen)]Cl·2H2O (1·2H2O) and [CoIII(pao)2(bpy)]Cl·1.5MeOH (2·1.5MeOH). The structures of the complexes were determined by single-crystal X-ray crystallography. The CoIII ions are six-coordinate, surrounded by three bidentate chelating ligands, that is, two pao− and one phen or bpy. The deprotonated oxygen atom of the pao− ligand remains uncoordinated and participates in hydrogen bonding with the solvate molecules. IR data of the complexes are discussed in terms of the nature of bonding and the known structures

Strategi Pengembangan USAha Agrowisata di Kebun Benih Hortikultura, Tohudan, Colomadu, Karanganyar

: The purpose of the research are to know the revenue in one year, knowing the factors internally and externally which became strengths, weaknesses, opportunities and threats, knowing a good alternative strategies to be formulated and know the priority good strategy to be applied in Kebun Benih Hortikultura Tohudan, Colomadu, Karanganyar. The basic methode of research is a descriptive analysis. Location of research in Kebun Benih Hortikultura Tohudan, Colomadu, Karanganyar. The data used are primary and secondary data. The analysis of the data used are (1) Revenue analysis, (2) Internal Factor Evaluation (IFE), (3) External Factor Evaluation (EFE), (4) SWOT, (5) QSPM. The result showed that income received by Kebun Benih Hortikultura Tohudan, Colomadu, Karanganyar in one year is Rp 65.766.000,00. Internal Factor Evaluation (IFE) showed the garden have six strengths and nine weaknesses. External Factor Evaluation (EFE) showed the garden have six opportunities and five threats. SWOT analysis showed the alternatives strategies that can be applied are utilize advances in technology information to promoting and marketing, building a relationship of cooperation with the investor, expand marketing production result and improve the situation of the garden to make it more interesting. QSPM showed a good strategy priorities to be applied is improve the situation of the garden to make it more interesting

A general synthetic route for the preparation of high-spin molecules: Replacement of bridging hydroxo ligands in molecular clusters by end-on azido ligands

Abstract A general method of increasing the ground-state total spin value of a polynuclear 3d-metal complex is illustrated through selected examples from cobalt(II) and nickel(II) cluster chemistry that involves the dianion of the gem-diol form of di-2-pyridyl ketone and carboxylate ions as organic ligands. The approach is based on the replacement of hydroxo bridges, that most often propagate antiferromagnetic exchange interactions, by the end-on azido ligand, which is a ferromagnetic coupler

Immune checkpoint inhibitor PD-1 pathway is down-regulated in synovium at various stages of rheumatoid arthritis disease progression.

Immune checkpoint blockade with therapeutic anti-cytotoxic T lymphocyte-associated antigen (CTLA)-4 (Ipilimumab) and anti-programmed death (PD)-1 (Nivolumab and Pembrolizumab) antibodies alone or in combination has shown remarkable efficacy in multiple cancer types, concomitant with immune-related adverse events, including arthralgia and inflammatory arthritis (IA) in some patients. Herein, using Nivolumab (anti-PD-1 antagonist)-responsive genes along with transcriptomics of synovial tissue from multiple stages of rheumatoid arthritis (RA) disease progression, we have interrogated the activity status of PD-1 pathway during RA development. We demonstrate that the expression of PD-1 was increased in early and established RA synovial tissue compared to normal and OA synovium, whereas that of its ligands, programmed death ligand-1 (PD-L1) and PD-L2, was increased at all the stages of RA disease progression, namely arthralgia, IA/undifferentiated arthritis, early RA and established RA. Further, we show that RA patients expressed PD-1 on a majority of synovial tissue infiltrating CD4+ and CD8+ T cells. Moreover, enrichment of Nivolumab gene signature was observed in IA and RA, indicating that the PD-1 pathway was downregulated during RA disease progression. Furthermore, serum soluble (s) PD-1 levels were increased in autoantibody positive early RA patients. Interestingly, most of the early RA synovium tissue sections showed negative PD-L1 staining by immunohistochemistry. Therefore, downregulation in PD-1 inhibitory signaling in RA could be attributed to increased serum sPD-1 and decreased synovial tissue PD-L1 levels. Taken together, these data suggest that agonistic PD1 antibody-based therapeutics may show efficacy in RA treatment and interception

Problem drug use the public health imperative: what some of the literature says

<p>Abstract</p> <p>Background</p> <p>With more than 200,000 problem drug users is contact with structured treatment services in England the public health imperative behind drug treatment is great. Problem drug use for many is a chronic and relapsing condition, where "cure" is often neither a reasonable or appropriate expectation and it can further be argued that in these circumstances problem drug use is no different from any number of chronic and enduring health conditions that are managed in the health care system and therefore should be conceptualised as such.</p> <p>Discussion</p> <p>A public health approach to drug treatment emphasises the need for drug users in or accessing treatment, to reduce their harmful drug use, reduce drug use related risks such as sepsis and overdose and stay alive for longer. However a public health perspective in relation to problem drug use isn't always either apparent or readily understood and to that end there is still a significant need to continue the arguments and debate that treatment and interventions for problem and dependent drug users need to extend beyond an individualistic approach. For the purposes of discussion in this article public and population health will be used interchangeably.</p> <p>Summary</p> <p>A recognition and acceptance that a public and population health approach to the management of problem drug users is sound public health policy also then requires a long term commitment in terms of staffing and resources where service delivery mirrors that of chronic condition management.</p

Juridification, new constitutionalism and market reforms to the English NHS

Market reforms to the English National Health Service within the neo-liberal era have diverted money away from patient needs to market bureaucracies and the coffers of private companies and undermine cross subsidy and risk pooling within the National Health Service. Consequently, governments within the neo-liberal era have sought to remove the deleterious effects of their market reforms from political contestation through strategies of depoliticisation. I assess the success of the strategies of juridification (the increase of formal law) and new constitutionalism (transnational legal rules which restrict national policymaking to the model of liberal democratic capitalism) in depoliticising market reforms to the English National Health Service. As the National Health Service was increasingly marketised, European Union public procurement and competition laws became increasingly applicable, although scope exists for exceptions. The discretion afforded to commissioners by the regulations passed pursuant to S.75 of the Health and Social Care Act (2012) regarding tendering is disputed. Many commissioners have acted as though their discretion was curtailed in practice. However, there are countervailing forces to competition, such as resource constraints and recent moves towards integration (although this may also afford private sector companies with new opportunities). I contend that the privatisation that marketisation has facilitated appears highly politicised, as is evidenced by increased campaigning activity in opposition to it. Recent responses to the Transatlantic Trade and Investment Partnership and prospective post-Brexit trade deals indicate a heightened awareness of the ability of external constitutional constraints to restrict National Health Service policymaking. This suggests that neither the strategies of juridification nor new constitutionalism have been successful in depoliticising market reforms to the English National Health Service

Preparation and characterization of [C6H5CH2NH3](2)PbI4, [C6H5CH2CH2SC(NH2)(2)](3)PbI5 and [C10H7CH2NH3]PbI3 organic-inorganic hybrid compounds

Journal URL: http://www.znaturforsch.com/b.ht