A general synthetic approach to hydroquinone meroterpenoids: stereoselective synthesis of (+)-(S)-metachromin V and alliodorol.

A new general synthetic approach to hydroquinone meroterpenoids is here described. The framework of the aforementioned natural compounds was built up through the Li2CuCl4 catalysed cross coupling reaction of the 4-substituted-( E)-prenyl acetates 9 with 2,5-bis(benzyloxy)phenyl magnesium bromide 8 as a key step. The latter sp3-sp2 coupling affords the products in good chemical yields and in very high stereoisomeric purity. A further key step of the present synthetic method consists of the removal of the benzylic protecting groups by a very mild procedure based on the use of lithium naphthalenide. The latter reagent, in combination with aliphatic dialkylamines, is able to cleave all the benzylic protecting groups leaving unaffected the polyenic moieties. By these means, we devised a new synthesis of the natural hydroquinone geranylhydroquinone, farnesylhydroquinone, metachromin V and alliodorol. In addition, the marine meroterpenoid, (+)-( S)-metachromin V, was synthesized for the first time; its chemical structure was confirmed and its absolute configuration was unambiguously assigned

Molecular screening for Midichloria bacteria in hard and soft ticks (Acari: Ixodida).

Ticks can harbor complex and highly variable microbial communities. Among these microorganisms,there are important pathogens of humans and animals that can be transmitted through the blood meal.Less is known about the other members of the microbial community of Ixodida, those that do not causeovert diseases. Among these, Midichloria mitochondrii, symbiont of the tick Ixodes ricinus, is the firstdescribed member of the family Midichloriaceae, order Rickettsiales. This bacterium is present in 100%females and is vertically transmitted (Sassera, 2008). The possibility of horizontal transmission issuggested by serological and molecular analyses showing positivity of mammalian blood and sera to M.mitochondrii (Mariconti, 2012; Bazzocchi, 2013). However, its role is still unknown. Recent reports areexpanding the view of this family, now including bacteria of great biological and medical interest,indicating a widespread distribution with an increasing range of hosts, with ticks being stronglyrepresented (Epis, 2008).Here we present a molecular screening of 17 tick species (for a total of 92 individuals), detecting andquantifying bacteria closely related to M. mitochondrii in seven of them, including the first report of amidichloriacea in a soft tick species, Ornithodoros maritimus. Based on sequence identity andphylogenetic analysis we propose that these bacteria could constitute the genus Midichloria. Theperformed screening highlights different prevalence levels in different tick species including one, Ixodesaulacodi, where the bacteria is present in all examined individuals, like in I. ricinus. This result promptsus to hypothesize different roles of Midichloria bacteria in different tick species

Performance evaluation of a tracking system for intermodal traffic: an experimentation in the Tyrrhenian area

Monitoring shipments along intermodal chains is crucial to ensuring the fast, reliable and secure transport of goods. In this regard, the paper describes the results of a real-life tracking experimentation carried out in June 2018 in the Tyrrhenian area with a twofold objective: 1) to evaluate the performance of a state-of-art tracking system to effectively monitor Ro-Ro freight units moving along intermodal chains; 2) to get an objective view of the intermodal chains currently connecting the two main Italian islands to the mainland. The experimentation was performed by means of a tracking device using the GSM network for data connection and geographical position detection. In addition, the Automatic Identification System (AIS) data were used to improve positioning during navigation. Quantitative analyses carried out on the recorded tracking data revealed that a significant share of the total transport time of the monitored transport chains is unproductive time that goods spend waiting at the port and logistics nodes. From a technical point of view, the experimentation raised several problems of the tracking technology employed vis-à-vis real-time tracking, continuous monitoring, signal coverage and positioning accuracy. A discussion of the main detected limitations is provided in the paper along with some possible solutions to overcome them

Failed Switching off in the MIBI-Parathyroid Scintigraphy in a Dialyzed Patient with Secondary Hyperparathyroidism Responsive to Cinacalcet Therapy

The aims of your case report is to show the predictivity of 99mTc-sestamibi (MIBI) scintigraphy and doppler ultrasound imaging on secondary hyperparathyroidism (SHPT) in a patient responsive to calcimimetic treatment. Moreover, it has been reported that calcimimetic has great potential in reducing the volume of the parathyroid gland. On the other hand, the MIBI scintigraphy is considered a crucial diagnostic procedure to monitor the response to therapy in terms of turnover and cellular metabolism; whereas, ultrasound to monitor the volume variation in response to treatment. It is described the case of a 73-year-old man on hemodialysis from 1995 for ESRD. Within 2 years the patient gradually developed SHPT with progressively increased iPTH up to 1,000 ρg/ml. The ultrasound, highlighted the presence of two parathyroid hyperplasia, confirmed by scintigraphy, showing focal increase uptake of sestamibi in the same anatomical areas. As a result of the patient's refusal to perform a parathyroidectomy, cinacalcet, was administered (65 mg overage daily dose). After a year of treatment, there was a striking decrease of iPTH (from 1300 to 57 ρg/ml, −95%); but, on the contrary to expectations, this positive metabolic outcome, was not followed by parathyroid changes in ultrasound and scintigraphic findings

The plasters of the Sacro Monte of Varallo Sesia. From the characterisation to the proposition of a restorative mix

Abstract In this paper, the systematic physical-chemical characterisation of historical plasters of the Sacro Monte of Varallo Sesia, Italy, the study of the local constructive techniques, as well as the evaluation of new restoration plasters is presented. The selected samples (from XVI to XVIIIth centuries) are in a quite good state of conservation despite the prolonged exposition to weathering agents. This behaviour is due to the good manufacturing and to the peculiar smooth finishing layers which reduce water permeability and allow water drops to slide off. The plasters characterisation realised in laboratory for in situ integration is also presented. These plasters should meet functional and aesthetical requirements and must satisfy the compatibility issues not only related to the physical-chemical aspects

DE NOVO "O PORTO É A PORTA": Breve per-curso literário do encontro entre a teologia e a antropologia presentes na prosa de Adélia Prado e de Clarice Lispector

O artigo a seguir apresenta uma análise sucinta das obras Uma aprendizagem ou O livro dos prazeres e A paixão segundo G.H., de Clarice Lispector e O homem da mão seca, de Adélia Prado, sob um elemento peculiar às três leituras: o encontro entre a questão antropológica - que demarca o conhecimento, o cuidado e a aceitação de si e do outro - e o pensamento teológico - que se manifesta no conhecimento de Deus (em Adélia, e do Deus, como Clarice costuma nomear), a partir da ‘humanidade do mais humano’ presente em ambas as obras. De fato, o texto bíblico do profeta Isaías ilustra o que se quer (d)escrever nas linhas abaixo, isto é, conseguir ver a Deus está intrínseca e corolariamente imbricado a ver-se a si mesmo: "ai de mim, que estou perdido! Pois sou homem de lábios impuros e habito no meio de um povo de impuros lábios, e os meus olhos viram ao Rei, o Senhor os Exércitos" (Is. 6,5). Eis o ‘encontro feliz’ de Adélia e Claric

Bipolar disorder and antithyroid antibodies: review and case series

Mood disorders and circulating thyroid antibodies are very prevalent in the population and their concomitant occurrence may be due to chance. However, thyroid antibodies have been repeatedly hypothesized to play a role in specific forms of mood disorders. Potentially related forms include treatment-refractory cases, severe or atypical depression, and depression at specific phases of a woman's life (early gestation, postpartum depression, perimenopausal). With regard to bipolar disorder, studies of specific subgroups (rapid cycling, mixed, or depressive bipolar) have reported associations with thyroid antibodies. Offspring of bipolar subjects were found more vulnerable to develop thyroid antibodies independently from the vulnerability to develop psychiatric disorders. A twin study suggested thyroid antibodies among possible endophenotypes for bipolar disorder. Severe encephalopathies have been reported in association with Hashimoto's thyroiditis. Cases with pure psychiatric presentation are being reported, the antithyroid antibodies being probably markers of some other autoimmune disorders affecting the brain. Vasculitis resulting in abnormalities in cortical perfusion is one of the possible mechanisms

New active site oriented glyoxyl-agarose derivatives of Escherichia coli penicillin G acylase

<p>Abstract</p> <p>Background</p> <p>Immobilized Penicillin G Acylase (PGA) derivatives are biocatalysts that are industrially used for the hydrolysis of Penicillin G by fermentation and for the kinetically controlled synthesis of semi-synthetic β-lactam antibiotics. One of the most used supports for immobilization is glyoxyl-activated agarose, which binds the protein by reacting through its superficial Lys residues. Since in <it>E. coli </it>PGA Lys are also present near the active site, an immobilization that occurs through these residues may negatively affect the performance of the biocatalyst due to the difficult diffusion of the substrate into the active site. A preferential orientation of the enzyme with the active site far from the support surface would be desirable to avoid this problem.</p> <p>Results</p> <p>Here we report how it is possible to induce a preferential orientation of the protein during the binding process on aldehyde activated supports. A superficial region of PGA, which is located on the opposite side of the active site, is enriched in its Lys content. The binding of the enzyme onto the support is consequently forced through the Lys rich region, thus leaving the active site fully accessible to the substrate. Different mutants with an increasing number of Lys have been designed and, when active, immobilized onto glyoxyl agarose. The synthetic performances of these new catalysts were compared with those of the immobilized wild-type (wt) PGA. Our results show that, while the synthetic performance of the wt PGA sensitively decreases after immobilization, the Lys enriched mutants have similar performances to the free enzyme even after immobilization.</p> <p>We also report the observations made with other mutants which were unable to undergo a successful maturation process for the production of active enzymes or which resulted toxic for the host cell.</p> <p>Conclusion</p> <p>The desired orientation of immobilized PGA with the active site freely accessible can be obtained by increasing the density of Lys residues on a predetermined region of the enzyme. The newly designed biocatalysts display improved synthetic performances and are able to maintain a similar activity to the free enzymes. Finally, we found that the activity of the immobilized enzyme proportionally improves with the number of introduced Lys.</p