Further Investigation of the Mediterranean Sponge Axinella polypoides: Isolation of a New Cyclonucleoside and a New Betaine

An exhaustive exploration into the metabolic content of the Mediterranean sponge Axinella-polypoides resulted in the isolation of the new betaine 5 and the new cyclonucleoside 8. The structures of the new metabolites were elucidated by spectroscopic methods assisted by computational methods. The analysis also provided evidence that the sponge does not elaborate pyrrole-imidazole alkaloids (PIAs) but, interestingly, it was shown to contain two already known cyclodipeptides, compounds 9 (verpacamide A) and 10

Nonabsorbable polymer clip as a cause of chronic perineal pain after radical prostatectomy: Description of a case treated by transperineal approach

The occurrence of persistent perineal pain caused by surgical clips has rarely been described after radical prostatectomy (RP). We describe the case of a patient complaining of chronic perineal pain occurred soon after robotic RP, refractory to conventional medical therapy and exacerbated by the sitting position. Pain was related to a nonabsorbable polymer clip used to secure lateral pedicles. A transpeerineal approach was used to perform an hydrodissection of the rectovesical space at the level of the surgical clip combined with local injection of mepivacaine and betametasone. The patient experienced a clinically significant reduction of pain that remained stable at three months' follow-up

Aplisulfamines, New Sulfoxide-Containing Metabolites from an Aplidium Tunicate: Absolute Stereochemistry at Chiral Sulfur and Carbon Atoms Assigned Through an Original Combination of Spectroscopic and Computational Methods

Two new sulfoxide-containing metabolites, aplisulfamines A (1) and B (2), have been isolated from an Aplidium sp. collected in the Bay of Naples. Their planar structure and geometry of a double bond were readily determined by using standard methods, mainly NMR spectroscopy. An original approach was used to assign the absolute configuration at the three contiguous chiral centers present in the structures of both aplisulfamines, two at carbon and one at sulfur. This involved Electronic Circular Dichroism (ECD) studies, J-based configuration analysis and Density Functional Theory (DFT) calculations and represents an interesting integration of modern techniques in stereoanalysis, which could contribute to the enhancement of theoretical protocols recently applied to solve stereochemical aspects in structure elucidation

Zorrimidazolone, a Bioactive Alkaloid from the Non-Indigenous Mediterranean Stolidobranch Polyandrocarpa zorritensis

Chemical analysis of the Mediterranean ascidian Polyandrocarpa zorritensis (Van Name 1931) resulted in the isolation of a series of molecules including two monoindole alkaloids, 3-indolylglyoxylic acid (3) and its methyl ester (4), 4-hydroxy-3-methoxyphenylglyoxylic acid methyl ester (1) and a new alkaloid we named zorrimidazolone (2). The structure of the novel compound 2 has been elucidated by spectroscopic analysis and bioactivity of all compounds has been investigated. Zorrimidazolone (2) showed a modest cytotoxic activity against C6 rat glioma cell line

Global variation in diabetes diagnosis and prevalence based on fasting glucose and hemoglobin A1c

Fasting plasma glucose (FPG) and hemoglobin A1c (HbA1c) are both used to diagnose diabetes, but these measurements can identify different people as having diabetes. We used data from 117 population-based studies and quantified, in different world regions, the prevalence of diagnosed diabetes, and whether those who were previously undiagnosed and detected as having diabetes in survey screening, had elevated FPG, HbA1c or both. We developed prediction equations for estimating the probability that a person without previously diagnosed diabetes, and at a specific level of FPG, had elevated HbA1c, and vice versa. The age-standardized proportion of diabetes that was previously undiagnosed and detected in survey screening ranged from 30% in the high-income western region to 66% in south Asia. Among those with screen-detected diabetes with either test, the age-standardized proportion who had elevated levels of both FPG and HbA1c was 29-39% across regions; the remainder had discordant elevation of FPG or HbA1c. In most low- and middle-income regions, isolated elevated HbA1c was more common than isolated elevated FPG. In these regions, the use of FPG alone may delay diabetes diagnosis and underestimate diabetes prevalence. Our prediction equations help allocate finite resources for measuring HbA1c to reduce the global shortfall in diabetes diagnosis and surveillance

Global variations in diabetes mellitus based on fasting glucose and haemogloblin A1c

Fasting plasma glucose (FPG) and haemoglobin A1c (HbA1c) are both used to diagnose diabetes, but may identify different people as having diabetes. We used data from 117 population-based studies and quantified, in different world regions, the prevalence of diagnosed diabetes, and whether those who were previously undiagnosed and detected as having diabetes in survey screening had elevated FPG, HbA1c, or both. We developed prediction equations for estimating the probability that a person without previously diagnosed diabetes, and at a specific level of FPG, had elevated HbA1c, and vice versa. The age-standardised proportion of diabetes that was previously undiagnosed, and detected in survey screening, ranged from 30% in the high-income western region to 66% in south Asia. Among those with screen-detected diabetes with either test, the agestandardised proportion who had elevated levels of both FPG and HbA1c was 29-39% across regions; the remainder had discordant elevation of FPG or HbA1c. In most low- and middle-income regions, isolated elevated HbA1c more common than isolated elevated FPG. In these regions, the use of FPG alone may delay diabetes diagnosis and underestimate diabetes prevalence. Our prediction equations help allocate finite resources for measuring HbA1c to reduce the global gap in diabetes diagnosis and surveillance.peer-reviewe

Un caso di miglioramento aziendale basato sull'applicazione della metodologia delle 5S : Siemens VDO Automative

Questo lavoro è stato svolto in collaborazione con la Siemens VDO Automative di Pisa e ha avuto come scopo l’applicazione della metodologia nell’area magazzino, nell’area componenti, e nelle aree PSQ Lab e laboratori metrologici negli stabilimenti produttivi di Fauglia e di San Piero a Grado e il mantenimento della metodologia all’interno dell’area Deka VII e Subassembly di Fauglia. L’applicazione della metodologia 5S in Siemens rientra nel progetto di “Totally Cleaning Injector”, pianificato e introdotto per affrontare e superare i problemi legati alla contaminazione presente nelle varie aree della clean room. L’applicazione quotidiana delle 5S ha consentito di migliorare lo stato di pulizia e di ordine all’interno delle varie aree, risolvendo in maniera positiva i problemi preliminarmente segnalati. Sono state svolte attività di audit regolari e valutazioni delle varie aree attraverso delle check list strutturate ad oc per ogni area, necessarie per monitorare e mantenere lo stato migliore di ordine e pulizia in ciascuna area

Chemical Diversity of the Mediterranean sponge Axinella polypoides

Among the multitude of marine organisms, some of them appear to possess a much more efficient synthetic potential. This capacity doesn’t represent the attribute of a single species, but it is shared by a number of other sponges, tunicates, bryozoans or molluscs. The consequent uncommon chemodiversity of these invertebrates is a resource to be adequately exploited. The extremely rich secondary metabolism of some marine invertebrates can be illustrated through the case of the sponge Axinella polypoides, whose chemical analysis, revealed an incredible variety and abundance of secondary metabolites, some of them being new molecues. The structures of all the isolated metabolites have been elucidated mainly by spectroscopic methods (HRESIMS, 2DNMR, ECD) with the support of computational methods

Aplisulfamines, Unique Natural Sulfoxides from Aplidium sp.: Assignment of Sulfur and Carbons Absolute Configuration through an Unprecedented Combination of Spectroscopic and Computational Methods

The occurrence of sulfoxides in nature is limited, being confined mostly to peptide derivatives containing methionine- or b,b-dimethylmethionine S-oxides, podolactones, metabolites from onions and from other Allium species as well as from a few marine organisms. In the frame of a research project devoted to the study of secondary metabolites of Mediterranean tunicates, we have isolated two novel natural sulfoxides, aplisulfamines A e B (1 and 2), from an Aplidium sp. collected in the Bay of Naples. In the present communication we report about the isolation and structure determination of these two unique compounds. The assignment of absolute configuration of chiral sulfur and carbon atoms present in the molecules 1 and 2 was achieved by an unprecedented approach based on a combination of NMR experiments and CD studies assisted by computational methods

Marine natural meroterpenes from Aplidium conicum: structures, synthesis and pharmacology

Meroterpenes are compounds of mixed biosynthesis, mostly quinones or hydroquinones bonded with a terpenoid portion. In the marine environment, these secondary metabolites are isolated mainly from brown algae, but other sources include microorganisms, soft corals and invertebrates. Among marine ascidians, they have been found almost exclusively in species belonging to the genus Aplidium, which have been the source of a vast array of prenyl-quinone, -hydroquinone, -chromene, and/or -chromane derivatives, either linear or cyclic, originated from intra- and inter-molecular cyclizations and/or rearrangements, thus giving macrocyclic or policyclic skeletons, often linked to amino acids or taurine residues. We have isolated from several collections of A. conicum a large group of unique meroterpenes. One of these compound has been used as model compound for the synthesis of synthetic analogues in which the prenyl chain is replaced by other alkyl chains; both the synthetic analogues and the natural metabolite were subjected to pharmacological screenings and were shown to possess interesting biological effects, depending on the nature and the length of side chain linked to the benzoquinone ring and, mainly, on its position respect to the dioxothiazine ring. Our studies revealed exemplify the potential of a natural product to qualify as lead structure for medicinal chemistry campaigns, affording simplified analogues with better bioactivity and easier to synthesize