Stereoselective synthesis of novel diels-alder adducts of p-substituted Methyl Thiocinnamates and Cyclopentadiene

This article describes the Diels-Alder reaction between methyl thiocinnamates, substituted at the para position by electron-donating and electron-withdrawing groups, with cyclopentadiene in the presence of catechol boron bromide (CBB) as a Lewis acid catalyst. The adduct configuration was confirmed by H-1 NMR coupling constants and single-crystal x-ray diffraction. Total endo stereoselectivity was observed in all reactions and was attributed to the effective secondary interaction between the boron atom and the incipient double bond in the norbonene resulting from the planar geometry of the catalyst. C-13 NMR chemical shifts of the coordinated dienophile carbonyl carbons with CBB compared to those of the non coordinated thiocinammates suggest a strong complexation with the catalyst.

Quantum field theory of (p,0)-forms on kaehler manifolds

In questa tesi abbiamo studiato la quantizzazione di una teoria di gauge di forme differenziali su spazi complessi dotati di una metrica di Kaehler. La particolarità di queste teorie risiede nel fatto che esse presentano invarianze di gauge riducibili, in altre parole non indipendenti tra loro. L'invarianza sotto trasformazioni di gauge rappresenta uno dei pilastri della moderna comprensione del mondo fisico. La caratteristica principale di tali teorie è che non tutte le variabili sono effettivamente presenti nella dinamica e alcune risultano essere ausiliarie. Il motivo per cui si preferisce adottare questo punto di vista è spesso il fatto che tali teorie risultano essere manifestamente covarianti sotto importanti gruppi di simmetria come il gruppo di Lorentz. Uno dei metodi più usati nella quantizzazione delle teorie di campo con simmetrie di gauge, richiede l'introduzione di campi non fisici detti ghosts e di una simmetria globale e fermionica che sostituisce l'iniziale invarianza locale di gauge, la simmetria BRST. Nella presente tesi abbiamo scelto di utilizzare uno dei più moderni formalismi per il trattamento delle teorie di gauge: il formalismo BRST Lagrangiano di Batalin-Vilkovisky. Questo metodo prevede l'introduzione di ghosts per ogni grado di riducibilità delle trasformazioni di gauge e di opportuni “antifields" associati a ogni campo precedentemente introdotto. Questo formalismo ci ha permesso di arrivare direttamente a una completa formulazione in termini di path integral della teoria quantistica delle (p,0)-forme. In particolare esso permette di dedurre correttamente la struttura dei ghost della teoria e la simmetria BRST associata. Per ottenere questa struttura è richiesta necessariamente una procedura di gauge fixing per eliminare completamente l'invarianza sotto trasformazioni di gauge. Tale procedura prevede l'eliminazione degli antifields in favore dei campi originali e dei ghosts e permette di implementare, direttamente nel path integral condizioni di gauge fixing covarianti necessari per definire correttamente i propagatori della teoria. Nell'ultima parte abbiamo presentato un’espansione dell’azione efficace (euclidea) che permette di studiare le divergenze della teoria. In particolare abbiamo calcolato i primi coefficienti di tale espansione (coefficienti di Seeley-DeWitt) tramite la tecnica dell'heat kernel. Questo calcolo ha tenuto conto dell'eventuale accoppiamento a una metrica di background cosi come di un possibile ulteriore accoppiamento alla traccia della connessione associata alla metrica.

Thermoelectric performance of p-type TiCoSb half-Heusler compounds - Intrinsic phase separation and charge carrier concentration optimization as key to high efficiency

The world's rising demand of energy turns the development of sustainable and more efficient technologies for energy production and storage into an inevitable task. Thermoelectric generators, composed of pairs of n-type and p-type semiconducting materials, di¬rectly transform waste heat into useful electricity. The efficiency of a thermoelectric mate¬rial depends on its electronic and lattice properties, summarized in its figure of merit ZT. Desirable are high electrical conductivity and Seebeck coefficients, and low thermal con¬ductivity. Half-Heusler materials are very promising candidates for thermoelectric applications in the medium¬ temperature range such as in industrial and automotive waste heat recovery. The advantage of Heusler compounds are excellent electronic properties and high thermal and mechanical stability, as well as their low toxicity and elemental abundance. Thus, the main obstacle to further enhance their thermoelectric performance is their relatively high thermal conductivity.rn rnIn this work, the thermoelectric properties of the p-type material (Ti/Zr/Hf)CoSb1-xSnx were optimized in a multistep process. The concept of an intrinsic phase separation has recently become a focus of research in the compatible n-type (Ti/Zr/Hf)NiSn system to achieve low thermal conductivities and boost the TE performance. This concept is successfully transferred to the TiCoSb system. The phase separation approach can form a significant alternative to the previous nanostructuring approach via ball milling and hot pressing, saving pro¬cessing time, energy consumption and increasing the thermoelectric efficiency. A fundamental concept to tune the performance of thermoelectric materials is charge carrier concentration optimization. The optimum carrier concentration is reached with a substitution level for Sn of x = 0.15, enhancing the ZT about 40% compared to previous state-of-the-art samples with x = 0.2. The TE performance can be enhanced further by a fine-tuning of the Ti-to-Hf ratio. A correlation of the microstructure and the thermoelectric properties is observed and a record figure of merit ZT = 1.2 at 710°C was reached with the composition Ti0.25Hf0.75CoSb0.85Sn0.15.rnTowards application, the long term stability of the material under actual conditions of operation are an important issue. The impact of such a heat treatment on the structural and thermoelectric properties is investigated. Particularly, the best and most reliable performance is achieved in Ti0.5Hf0.5CoSb0.85Sn0.15, which reached a maximum ZT of 1.1 at 700°C. The intrinsic phase separation and resulting microstructure is stable even after 500 heating and cooling cycles.

Appropriateness of reporting statistical results in orthodontics: the dominance of P values over confidence intervals

The purpose of this study was to search the orthodontic literature and determine the frequency of reporting of confidence intervals (CIs) in orthodontic journals with an impact factor. The six latest issues of the American Journal of Orthodontics and Dentofacial Orthopedics, the European Journal of Orthodontics, and the Angle Orthodontist were hand searched and the reporting of CIs, P values, and implementation of univariate or multivariate statistical analyses were recorded. Additionally, studies were classified according to the type/design as cross-sectional, case-control, cohort, and clinical trials, and according to the subject of the study as growth/genetics, behaviour/psychology, diagnosis/treatment, and biomaterials/biomechanics. The data were analyzed using descriptive statistics followed by univariate examination of statistical associations, logistic regression, and multivariate modelling. CI reporting was very limited and was recorded in only 6 per cent of the included published studies. CI reporting was independent of journal, study area, and design. Studies that used multivariate statistical analyses had a higher probability of reporting CIs compared with those using univariate statistical analyses. Misunderstanding of the use of P values and CIs may have important implications in implementation of research findings in clinical practice.

Equality of P-partition Generating Functions

To every partially ordered set (poset), one can associate a generating function, known as the P-partition generating function. We find necessary conditions and sufficient conditions for two posets to have the same P-partition generating function. We define the notion of a jump sequence for a labeled poset and show that having equal jumpsequences is a necessary condition for generating function equality. We also develop multiple ways of modifying posets that preserve generating function equality. Finally, we are able to give a complete classification of equalities among partially ordered setswith exactly two linear extensions.

Clearance of p-cresol sulfate and β-2-microglobulin from dialysate by commercially available sorbent technology

Dialysate regeneration by sorbents is an alternative to conventional single-pass dialysis. Little is known about the capacity of sorbents to clear dialysate of “middle molecules” and protein-bound uremic toxins. We studied p-cresol sulfate (PCS) and β-2-microglobulin (β2M) removal from dialysate by a sorbent: 1. PCS (40 mg PCS dissolved in 4 L of fresh dialysate) was recirculated through a sorbent cartridge (SORB Technology, Inc.) for analysis of PCS removal. 2. Spent peritoneal dialysate was recirculated on the “blood” side of a high-flux dialyzer. On the “dialysate” side of the membrane, bicarbonate dialysate was recirculated through a sorbent cartridge. β2M was measured in both streams. Two results are of particular importance for the use of regenerated fluid in chronic dialysis: 1. PCS was virtually completely removed from the dialysate. On average, PCS concentration was reduced to 1.4% of the starting concentration after 60 minutes. PCS extraction across the sorbent was nearly complete at any time. 2. β2M was on average reduced to 14.3% of the starting concentration after 60 minutes. Postsorbent concentrations were consistently below the validated range of the test method. We conclude that PCS and β2M are efficiently removed from the dialysate by commercially available sorbent technology. Spent peritoneal dialysis fluid can be cleared of β2M when circulated against sorbent-regenerated dialysate using a high-flux membrane.

Dephosphorylation of p-ERK1/2 in relation to tumor remission after HER-2 and Raf1 blocking therapy in a conditional mouse tumor model

Several studies have shown that HER-2/neu (erbB-2) blocking therapy strategies can cause tumor remission. However, the responsible molecular mechanisms are not yet known. Both ERK1/2 and Akt/PKB are critical for HER-2-mediated signal transduction. Therefore, we used a mouse tumor model that allows downregulation of HER-2 in tumor tissue by administration of anhydrotetracycline (ATc). Switching-off HER-2 caused a rapid tumor remission by more than 95% within 7 d of ATc administration compared to the volume before switching-off HER-2. Interestingly, HER-2 downregulation caused a dephosphorylation of p-ERK1/2 by more than 80% already before tumor remission occurred. Levels of total ERK protein were not influenced. In contrast, dephosphorylation of p-Akt occurred later, when the tumor was already in remission. These data suggest that in our HER-2 tumor model dephosphorylation of p-ERK1/2 may be more critical for tumor remission than dephosphorylation of p-Akt. To test this hypothesis we used a second mouse tumor model that allows ATc controlled expression of BXB-Raf1 because the latter constitutively signals to ERK1/2, but cannot activate Akt/PKB. As expected, downregulation of BXB-Raf1 in tumor tissue caused a strong dephosphorylation of p-ERK1/2, but did not decrease levels of p-Akt. Interestingly, tumor remission after switching-off BXB-Raf1 was similarly efficient as the effect of HER-2 downregulation, despite the lack of p-Akt dephosphorylation. In conclusion, two lines of evidence strongly suggest that dephosphorylation of p-ERK1/2 and not that of p-Akt is critical for the rapid tumor remission after downregulation of HER-2 or BXB-Raf1 in our tumor model: (i) dephosphorylation of p-ERK1/2 but not that of p-Akt precedes tumor remission after switching-off HER-2 and (ii) downregulation of BXB-Raf1 leads to a similarly efficient tumor remission as downregulation of HER-2, although no p-Akt dephosphorylation was observed after switching-off BXB-Raf1.

Age and gender-dependent alternative splicing of P/Q-type calcium channel EF-hand

Ca(v)2.1 Ca(2+) channels (P/Q-type), which participate in various key roles in the CNS by mediating calcium influx, are extensively spliced. One of its alternatively-spliced exons is 37, which forms part of the EF hand. The expression of exon 37a (EFa form), but not exon 37b (EFb form), confers the channel an activity-dependent enhancement of channel opening known as Ca(2+)-dependent facilitation (CDF). In this study, we analyzed the trend of EF hand splice variant distributions in mouse, rat and human brain tissues. We observed a developmental switch in rodents, as well as an age and gender bias in human brain tissues, suggestive of a possible role of these EF hand splice variants in neurophysiological specialization. A parallel study performed on rodent brains showed that the data drawn from human and rodent tissues may not necessarily correlate in the process of aging.

Aneurysmal bone cyst of the tuberculum articulare of the temporomandibular joint: a case report

A case is presented of a 14-year-old boy with aneurysmal bone cyst of the tuberculum articulare of the temporomandibular joint (TMJ). This disease rarely involves the skull, and involvement of temporal bone is even more rare. To our knowledge, only 22 cases have been reported in the literature. This is the first case of aneurysmal bone cyst of the tuberculum articulare of the TMJ described in the literature.

Surgical approach for synovial cyst of the atlantoaxial joint: a case report and review of the literature

STUDY DESIGN: Case report and review of the literature. OBJECTIVE: We describe the first case of a synovial cyst arising from pseudarthrosis of a previous dens fracture. The literature is reviewed and etiological, diagnostic, and therapeutic options of atlantoaxial cysts are discussed. SUMMARY OF BACKGROUND DATA: Symptomatic synovial cysts of the atlantoaxial joint are rare. To the authors' knowledge only 24 cases have been reported.A 60-year-old patient presented with bilateral hand numbness, quadrihyperreflexia, and gait deterioration. Magnetic resonance imaging of the cervical spine disclosed a cystic mass located at the transverse ligament of dens axis causing bulbomedullary compression. METHODS: Surgery was performed via transoral image guided approach. The ventral atlas arch, dens, transverse ligament, tectorial membrane, and the compressing cyst were removed, followed by a C0-C3 fusion. RESULTS: Two months postsurgery the patient recovered completely from the cervical myelopathy with transient remnant dysparesthesia of the finger tips. CONCLUSION: Magnetic resonance imaging findings are not specific enough to establish a preoperative diagnosis. Radical resection via image-guided transoral route followed by posterior fusion allows complete resection of the cystic lesion and results in excellent long-term decompression.