Stereocontrolled synthesis and functionalization of cyclobutanes and cyclobutanones

In the last decade a certain number of new cyclobutane and cyclobutanone synthesis and functionalization protocols have been published. Organo- and biocatalyzed eco-friendly approaches to cyclobutane-containing molecules have been developed with interesting results. Also, successful new total synthesis of bioactive compounds and drugs have been recently reported where a four membered ring represented the key intermediate. Therefore, the rising interest in this field represents a great point of discussion for the scientific community, disclosing the synthetic potential of strained four membered ring carbocyclic compounds. Herein we report a critical survey on the literature concerning the enantiocontrolled synthesis and functionalization of cyclobutane derivatives, with particular attention to metal-free, low impact methodologies, published during the period 2000–2013

Tandem Baeyer–Villiger/Wittig/oxa-Michael addition: One-step to 5-substituted γ-lactones

The results reported in this study provide a practical protocol for the construction, in one single step of synthetically important γ-lactones in good yields starting from α-hydroxy cyclobutanone, H2O2 and several stabilized phosphonium ylides. Our synthetic strategy relies on a tandem Baeyer–Villiger oxidation/Wittig reaction/oxa-Michael addition

Reverse cycle chewing before and after orthodontic-surgical correction in class III patients.

Objective: The aim of this study was to investigate the prevalence of reverse-sequence chewing cycles in skeletal class III patients before and after orthodontic-surgical therapy to evaluate whether the occlusal and skeletal correction is followed by a functional improvement. Study Design: Twenty skeletal class III patients (11 males and 9 females, 22.7 ± 3.0 years old) were recruited for this study. All patients received orthodontic and surgical treatment. Chewing cycles were recorded with a kinesiograph before (T0) and after (T1) therapy. Results: A significant decrease in the number of reverse chewing cycles after surgical correction was exhibited in all recordings, when chewing either soft or hard boluses, on both the right and the left side. Conclusions: Evaluation of the prevalence of reverse chewing cycles could be considered an indicator of functional adaptation after therapy and a method for the early detection of nonresponding patients who may require further consideration using a different approach

Internal characterization of embankment dams using ground penetrating radar (GPR) and thermographic analysis: A case study of the Medau Zirimilis Dam (Sardinia, Italy)

The stability of embankment dams without an impermeable core depends on the characteristics of the face slab that prevents internal erosion, piping and eventual collapse of the structure. Under a Mediterranean climate, the impermeable asphaltic face slab is subjected to high solar radiation and consequent temperature changes, which can generate the creation of cracks and joints. The Medau Zirimilis Dam, located in the Casteddu River (Sardinia), is an embankment dam that has undergone seepage and continuous repairs in its asphalt face slab. These reparations have been conducted because of the occurrence of cracks and relative movement of different segments of the slab. To evaluate if seepage endangers the integrity of the dam, GPR was used, with different antennas (100, 250 and 500 MHz), along its crest and upstream and downstream faces, and the data were integrated with infrared thermographic images. Although geophysical data do not show structural changes affecting the main dam structure, deformation structures at shallow levels and in particular in the upstream face and along the crest of the dam have been identified. Such deformation affects the road atop the crest, the face slab and underlying levels, resulting in landslides that include material from several meters below the surface. The analysis permitted the identification of the origin of surficial cracks and their effects on the face slab. These sectors, independent of current movement, define the most unstable areas against water level changes that can affect the dam integrity. GPR analysis at the embankments usually has the handicap of high clay content that precludes electromagnetic wave penetration; however, in this case, the obtained resolution and extent of penetration using the different antennas was sufficient, due to the absence of an inner waterproof unit, and permitted the evaluation of the inner structure of the dam and the application of GPR for construction quality surveillance, internal structural characterization and dam monitoring

Axiography and MRI in the diagnosis of temporomandibular joint pathology

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Solvent-Free Synthesis of Quaternary Oxazolidine-2-thione β3-Amino Ester Analogs

A solvent-free organocatalyzed intermolecular cyclization reaction starting from β-substituted γ-hydroxy-α,β-unsaturated esters and aryl isothiocyanates proceeds via an aza-Michael addition to provide previously unknown quaternary oxazolidine-2-thione β3 amino ester analogs. A panel of diversely-substituted esters was investigated, including β,γ-disubstituted examples which provided the target molecules with very high cis diastereoselectivity

Synthesis of cyclobutane-fused oxazolidine-2-thione derivatives

An expedient, solvent-free, mild base catalyzed intermolecular cyclization reaction has been developed to enable the one-pot synthesis of fourteen examples of cyclobutane-fused oxazolidine-2-thiones in good to high yields. Bicyclic structures of this type have not previously been described in the literature; they have a cis ring junction with both rings deviating slightly from planarity

Age- and sex-related variations in platelet count in Italy: a proposal of reference ranges based on 40987 subjects' data

BACKGROUND AND OBJECTIVES: Although several studies demonstrated that platelet count is higher in women, decreases with age, and is influenced by genetic background, most clinical laboratories still use the reference interval 150-400×10(9) platelets/L for all subjects. The present study was to identify age- and sex-specific reference intervals for platelet count. METHODS: We analysed electronic records of subjects enrolled in three population-based studies that investigated inhabitants of seven Italian areas including six geographic isolates. After exclusion of patients with malignancies, liver diseases, or inherited thrombocytopenias, which could affect platelet count, reference intervals were estimated from 40,987 subjects with the non parametric method computing the 2.5° and 97.5° percentiles. RESULTS: Platelet count was similar in men and women until the age of 14, but subsequently women had steadily more platelets than men. The number of platelets decreases quickly in childhood, stabilizes in adulthood, and further decreases in oldness. The final result of this phenomenon is that platelet count in old age was reduced by 35% in men and by 25% in women compared with early infancy. Based on these findings, we estimated reference intervals for platelet count ×10(9)/L in children (176-452), adult men (141-362), adult women (156-405), old men (122-350) and, old women (140-379). Moreover, we calculated an extended reference interval that takes into account the differences in platelet count observed in different geographic areas. CONCLUSIONS: The age-, sex-, and origin-related variability of platelet count is very wide, and the patient-adapted reference intervals we propose change the thresholds for diagnosing both thrombocytopenia and thrombocytosis in Italy

Insights into the reactivity of 2-hydroxycyclobutanones with thiols corroborated by quantum chemical DFT investigations, NMR and Raman analysis

A general strategy for the synthesis of 2-substituted cyclobutanone sulfides via a tandem Br nsted acid-catalyzed nucleophile addition/ring contraction/C3-C4 ring expansion reaction sequence has been exploited. The procedure led to a wide panel of four-membered cyclic ketones in good to excellent yields and with broad substrate scope. Mechanistic aspects and kinetic parameters were investigated by quantum chemical DFT calculations, allowing us to rationalize the different reactivity of 2-aryl- and 2-alkyl-substituted 2-hydroxycyclobutanones towards thiol nucleophiles in reactions mediated by sulfonic acids. NMR and in situ Raman techniques were employed to better understand the reaction kinetics and parameters that affect the desired outcome

Maturity-Onset Diabetes of the Young in Children With Incidental Hyperglycemia:: A multicenter Italian study of 172 families

OBJECTIVE - To investigate the prevalence of maturity-onset diabetes of the young (MODY) in Italian children With incidental hyperglycemia. RESEARCH DESIGN AND METHODS - Among 748 subjects age 1-18 years with incidental hyperglycemia, minimal diagnostic criteria for MODY were met by 172 families. Mutational analyses of the glucokinase (GCK) and hepatocyte nuclear factor lot (HNF1A) genes were performed. RESULTS - We identified 85 GCK gene mutations in 109 probands and 10 HNF1A mutations in 12 probands. In GCK patients, the median neonatal weight and age at the first evaluation were lower than those found in patients with HNF1A mutations. Median fasting plasma glucose and impaired fasting glucose/impaired glucose tolerance frequency after oral glucose tolerance testing were higher in GCK patients, who also showed a lower frequency of diabetes than HNF1A patients. CONCLUSIONS - GCK mutations are the prevailing cause of MODY (63.4%) when the index case is recruited in Italian children with incidental hyperglycemia