[PdCl2{8-(di-tert-butylphosphinooxy)quinoline)}]: a highly efficient catalyst for Suzuki-Miyaura reaction

The complex [PdCl2(P-N)] containing the basic and sterically demanding 8-(di-tert-butylphosphinooxy)quinoline ligand (P-N) is a highly efficient catalyst for the coupling of phenylboronic acid with aryl bromides or aryl chlorides. The influence of solvent and base has been investigated, the highest rates being observed at 110 C in toluene with K2CO3 as the base. With aryl bromides the reaction rates are almost independent on the electronic properties of the para aryl substituents, on the contrary, reduced reaction rates are observed when bulky substituents are present on the substrate. Nevertheless the coupling of 2-bromo-1,3,5-trimethylbenzene with phenylboronic acid can be carried out to completion in 2 h using a catalyst loading of 0.02 mol %. Under optimized reaction conditions, turnover frequencies as high as 1900 h(-1) can be obtained in the coupling of 4-chloroacetophenone with phenylboronic acid: lower reaction rates are obtained with Substrates bearing EDG substituents on the aryl group. (C) 2009 Elsevier Ltd. All rights reserved

Demographic genetics of the endangered Amiata donkey breed

The demogenetic structure of the Amiata donkey, an endangered breed from Central Italy, was investigated using information from pedigrees. Genealogical data of 602 donkeys reared in Tuscany were recorded in a database and analysed by the computer package ENDOG. Population size increased from 89 subjects in 1995 to 503 (129 males and 374 females) in 2005. Animals were distributed among 152 herds, but the effective number of herds was 21, suggesting that a small number of herds provided stallions for the entire breed. The maximum number of traced generation was 4, the mean maximum generation was 1.14, the mean com- plete generation was 0.53, and the mean equivalent generation was 0.78. The average relatedness coeffi- cient (AR) in the 503 alive animals was 0.94% while the mean F was 0.29% so the effective population size was 172.41. Among 24 animals with a 4-generation history, 3 (12.5%) were 25% inbred. Although the incompleteness of genealogical information did not permit accurate inference of the current values of popu- lation genetic parameters, the present work represents a first step towards an efficient management of the breed

Role of IFN-gamma and IL-6 in a protective immune response to Yersinia enterocolitica in mice

<p>Abstract</p> <p>Background</p> <p><it>Yersinia </it>outer protein (Yop) H is a secreted virulence factor of <it>Yersinia enterocolitica </it>(Ye), which inhibits phagocytosis of Ye and contributes to the virulence of Ye in mice. The aim of this study was to address whether and how YopH affects the innate immune response to Ye in mice.</p> <p>Results</p> <p>For this purpose, mice were infected with wild type Ye (pYV⁺) or a YopH-deficient Ye mutant strain (Δ<it>yopH</it>). CD11b⁺cells were isolated from the infected spleen and subjected to gene expression analysis using microarrays. Despite the attenuation of Δ<it>yopH in vivo</it>, by variation of infection doses we were able to achieve conditions that allow comparison of gene expression in pYV⁺and Δ<it>yopH </it>infection, using either comparable infection courses or splenic bacterial burden. Gene expression analysis provided evidence that expression levels of several immune response genes, including IFN-γ and IL-6, are high after pYV⁺infection but low after sublethal Δ<it>yopH </it>infection. In line with these findings, infection of IFN-γR^-/-and IL-6^-/-mice with pYV⁺or Δ<it>yopH </it>revealed that these cytokines are not necessarily required for control of Δ<it>yopH</it>, but are essential for defense against infection with the more virulent pYV⁺. Consistently, IFN-γ pretreatment of bone marrow derived macrophages (BMDM) strongly enhanced their ability in killing intracellular Ye bacteria.</p> <p>Conclusion</p> <p>In conclusion, this data suggests that IFN-γ-mediated effector mechanisms can partially compensate virulence exerted by YopH. These results shed new light on the protective role of IFN-γ in Ye wild type infections.</p

Genetic variability of three local cattle breeds (Calvana, Pontremolese, Garfagnina) by STR analysis

AbstractThe dramatic size contraction of local cattle breeds due to replacement with cosmopolite improved breeds highlights the need for native genetic resources conservation. In 1985, the Anagraphic Register of local cattle breeds and small-size ethnic groups was established by the Italian Ministry of Agriculture and Forestry. Calvana, Pontremolese and Garfagnina are among the included breeds. They are all native from Tuscany. Present breeding area covers the provinces of Firenze, Prato, Pistoia and Siena for the Calvana breed (around 280 heads), while it is restricted to the province of Lucca for both Garfagnina (around 180 heads) and Pontremolese. This latter breed consists, nowadays, of less than 40 heads, while being around 15000 in 1940s.The characterization of the genetic structure and variability via molecular markers could provide useful information for breed management and conservation. In the present study, a total of 149 animals, evenly distributed among the three breeds, were genetically char..

Mechanistic understanding of chromium-based oligomerisation catalysts : an EPR and ENDOR investigation

Electron Paramagnetic Resonance (EPR) and Electron Nuclear Double Resonance (ENDOR) spectroscopies have been used to study the fundamental nature of chromium-based selective oligomerisation catalysts. A series of 'pre-catalyst' complexes were fully characterised CW-EPR revealed each complex to possess an axial g matrix (g > ge > g ) and superhyperfine coupling to two equivalent 31P nuclei, consistent with a low-spin cf species of approximate Cjv symmetry, where the metal contribution to the SOMO is primarily dxy. The isotropic component to the 31P coupling was of a larger magnitude in those Cr(I) complexes bearing PNP ligands than those bearing PCP, indicating that the phosphorus 3s character in the SOMO was higher for the former. CW-ENDOR demonstrated that subtle structural differences in the complexes, namely in the phenyl ring conformations, occurred as a function of ligand type. Pulsed experiments proved that the technique is valid and viable for further work on the activated system. Upon activation of the pre-catalyst with an alkylaluminium, four distinct paramagnetic centres were identified. A Cr(I) bis-arene complex was firstly detected it was found to form either via intramolecular co-ordination of the ligand phenyl groups, or preferentially via solvent-based arene co-ordination, if such groups were available. Two further species (I and III) were subsequently observed at low temperatures the spin Hamiltonian parameters extracted for both showed that a significant modification to the structure of the pre-catalyst had occurred. Half-field transitions indicated the possibility of a dimeric nature to Species III. ENDOR measurements detected an exceptionally large proton coupling in the activated system, possibly due to the co ordination of alkyl fragments to the metal centre. A final, fourth paramagnetic centre (Species IV), was detected and classed as an intermediate species, due to the greater similarity between its g and A matrices with those of the parent complex, than the other activated species. Finally, a preliminary investigation into analogous pre-catalyst complexes bearing N-heterocyclic carbene ligands was performed, due to their similar employment in oligomerisation catalysis CW-EPR spectra revealed information on both their electronic and structural natures.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

A Lentiviral Vector-Based, Herpes Simplex Virus 1 (HSV-1) Glycoprotein B Vaccine Affords Cross-Protection against HSV-1 and HSV-2 Genital Infections

Genital herpes is caused by herpes simplex virus 1 (HSV-1) and HSV-2, and its incidence is constantly increasing in the human population. Regardless of the clinical manifestation, HSV-1 and HSV-2 infections are highly transmissible to sexual partners and enhance susceptibility to other sexually transmitted infections. An effective vaccine is not yet available. Here, HSV-1 glycoprotein B (gB1) was delivered by a feline immunodeficiency virus (FIV) vector and tested against HSV-1 and HSV-2 vaginal challenges in C57BL/6 mice. The gB1 vaccine elicited cross-neutralizing antibodies and cell-mediated responses that protected 100 and 75% animals from HSV-1- and HSV-2-associated severe disease, respectively. Two of the eight fully protected vaccinees underwent subclinical HSV-2 infection, as demonstrated by deep immunosuppression and other analyses. Finally, vaccination prevented death in 83% of the animals challenged with a HSV-2 dose that killed 78 and 100% naive and mock-vaccinated controls, respectively. Since this FLY vector can accommodate two or more HSV immunogens, this vaccine has ample potential for improvement and may become a candidate for the development of a truly effective vaccine against genital herpes

To respond or not to respond - a personal perspective of intestinal tolerance

For many years, the intestine was one of the poor relations of the immunology world, being a realm inhabited mostly by specialists and those interested in unusual phenomena. However, this has changed dramatically in recent years with the realization of how important the microbiota is in shaping immune function throughout the body, and almost every major immunology institution now includes the intestine as an area of interest. One of the most important aspects of the intestinal immune system is how it discriminates carefully between harmless and harmful antigens, in particular, its ability to generate active tolerance to materials such as commensal bacteria and food proteins. This phenomenon has been recognized for more than 100 years, and it is essential for preventing inflammatory disease in the intestine, but its basis remains enigmatic. Here, I discuss the progress that has been made in understanding oral tolerance during my 40 years in the field and highlight the topics that will be the focus of future research

Association of Impulsivity and Polymorphic MicroRNA-641 Target Sites in the SNAP-25 Gene.

Impulsivity is a personality trait of high impact and is connected with several types of maladaptive behavior and psychiatric diseases, such as attention deficit hyperactivity disorder, alcohol and drug abuse, as well as pathological gambling and mood disorders. Polymorphic variants of the SNAP-25 gene emerged as putative genetic components of impulsivity, as SNAP-25 protein plays an important role in the central nervous system, and its SNPs are associated with several psychiatric disorders. In this study we aimed to investigate if polymorphisms in the regulatory regions of the SNAP-25 gene are in association with normal variability of impulsivity. Genotypes and haplotypes of two polymorphisms in the promoter (rs6077690 and rs6039769) and two SNPs in the 3' UTR (rs3746544 and rs1051312) of the SNAP-25 gene were determined in a healthy Hungarian population (N = 901) using PCR-RFLP or real-time PCR in combination with sequence specific probes. Significant association was found between the T-T 3' UTR haplotype and impulsivity, whereas no association could be detected with genotypes or haplotypes of the promoter loci. According to sequence alignment, the polymorphisms in the 3' UTR of the gene alter the binding site of microRNA-641, which was analyzed by luciferase reporter system. It was observed that haplotypes altering one or two nucleotides in the binding site of the seed region of microRNA-641 significantly increased the amount of generated protein in vitro. These findings support the role of polymorphic SNAP-25 variants both at psychogenetic and molecular biological levels