Metallkomplexe mit sterisch anspruchsvollen mono- und bifunktionellen Triazenidoliganden

Monoanionische, stickstoffhaltige Chelatliganden sind sehr populär und werden oft als Baueinheiten zur Synthese von Metallkomplexen eingesetzt. Im Gegensatz zu den bekannten Amidinat- und β-Diketiminatliganden wurde den Triazeniden bisher weniger Aufmerksamkeit geschenkt. Dies liegt hauptsächlich daran, dass wenige, sterisch anspruchsvolle Vertreter dieser Gruppe bekannt waren. Mit der Synthese neuer biphenyl- und terphenylsubstituierter Triazenide sind diese stärker in den Fokus der Forschung gerückt. Durch die Sperrigkeit der Liganden werden unerwünschte Ligandenumverteilungsreaktionen unterdrückt und der Weg zu neuen Metallkomplexen mit bemerkenswerten Eigenschaften geebnet. Diese Arbeit beschäftigt sich mit Triazenidokomplexen der Alkalimetalle, des Magnesiums, des Zinks und des Aluminiums. Zusätzlich zu den monofunktionellen wurden bifunktionelle Triazene, welche aus einer Biphenylgruppe aufgebaut sind und zwei terphenylsubstituierte Triazengruppen tragen, synthetisiert und deren Funktion als Komplexliganden untersucht. Durch das hohe Volumen der Liganden konnten Metallkomplexe hergestellt werden, die bemerkenswerte strukturelle Eigenschaften aufweisen. So bilden beispielsweise alle dargestellten Verbindungen Kristalle, die aus monomeren Baueinheiten aufgebaut sind. Eine homoleptische Magnesiumverbindung mit zwei Triazenidliganden weist eine ungewöhnliche, planare Koordinationssphäre auf, eine Triazenidodiphenylaluminiumverbindung zeigt eine interessante Ausrichtung der Phenylgruppen, die auf π-Stapeleffekte zurückgeführt wird und die Alkalimetalltriazenide weisen sekundäre Metall-π-Aren-Wechselwirkungen auf, womit eine bessere koordinative Absättigung des Koordinationszentrums erreicht wird. Zusätzlich zur strukturellen Charakterisierung mittels Röntgendiffraktometrie wurden, wo es möglich war 1H und 13C NMR-Messungen durchgeführt, Schmelzpunkte bestimmt sowie IR- und UV-VIS-Spektren aufgenommen. Durch die hohe Dichte an aromatischen Systemen innerhalb der Verbindungen, ist es bei einer dreikernigen Zinktriazenidverbindung gelungen mittels 1H NMR-Messungen die starken Einflüsse des Ringstroms nachzuweisen. Außerdem wurden DFT-Berechnungen durchgeführt, um herauszufinden, wie sehr die räumliche Ausrichtung der Bi- bzw. Terphenylsubstituenten gegenüber der N3-Baugruppe der Triazenide die Verteilung der negativen Ladung innerhalb eines monoanionischen Triazenids und somit dessen Koordinationseigenschaften beeinflusst. Diese Effekte konnten durch experimentelle Ergebnisse unterstützt werden.

"Mono No Aware" di Ken Liu: proposta di traduzione

Il lavoro consiste della traduzione di "Mono No Aware", racconto breve fantascientifico scritto da Ken Liu, vincitore degli Hugo Awards 2013, e dell'analisi della stessa. Nelle prime due sezioni dell'elaborato ho presentato l'autore, parlando dei suoi studi e dei suoi lavori, e il testo, parlando dei suoi temi e delle sue particolarità. Ho poi proseguito presentando la traduzione, ovvero i criteri su cui mi sono basato affinché il lavoro fosse di buona qualità. In seguito ho inserito la traduzione già corretta e revisionata e dopo di essa il commento, in cui ho evidenziato i punti problematici e le soluzioni trovate, corredate di esempi. Nelle conclusioni ho scritto le mie riflessioni sul lavoro eseguito, e infine ho aggiunto la sitografia e la bibliografia, seguite dal testo originale in appendice.

Performance of the pediatric-sized i-gel compared with the Ambu AuraOnce laryngeal mask in anesthetized and ventilated children

This prospective, randomized, controlled trial compares the performance of the pediatric i-gel (Intersurgical Ltd., Wokingham, United Kingdom) with the Ambu AuraOnce laryngeal mask (Ambu A/S, Ballerup, Denmark) in anesthetized and ventilated children.

Functionalization of deproteinized bovine bone with a coating-incorporated depot of BMP-2 renders the material efficiently osteoinductive and suppresses foreign-body reactivity

The repair of critical-sized bony defects remains a challenge in the fields of implantology, maxillofacial surgery and orthopaedics. As an alternative bone-defect filler to autologous bone grafts, deproteinized bovine bone (DBB) is highly osteoconductive and clinically now widely used. However, this product suffers from the disadvantage of not being intrinsically osteoinductive. In the present study, this property was conferred by coating DBB with a layer of calcium phosphate into which bone morphogenetic protein 2 (BMP-2) was incorporated. Granules of DBB bearing a coating-incorporated depot of BMP-2--together with the appropriate controls (DBB bearing a coating but no BMP-2; uncoated DBB bearing adsorbed BMP-2; uncoated DBB bearing no BMP-2)--were implanted subcutaneously in rats. Five weeks later, the implants were withdrawn for a histomorphometric analysis of the volume densities of (i) bone, (ii) bone marrow, (iii) foreign-body giant cells and (iv) fibrous capsular tissue. Parameters (i) and (ii) were highest, whilst parameters (iii) and (iv) were lowest in association with DBB bearing a coating-incorporated depot of BMP-2. Hence, this mode of functionalization not only confers DBB with the property of osteoinductivity but also improves its biocompatibility--thus dually enhancing its clinical potential in the repair of bony defects.

Does quantification of USPIO uptake-related signal loss allow differentiation of benign and malignant normal-sized pelvic lymph nodes?

Ultrasmall superparamagnetic iron oxide (USPIO) particles are promising contrast media, especially for molecular and cellular imaging besides lymph node staging owing to their superior NMR efficacy, macrophage uptake and lymphotropic properties. The goal of the present prospective clinical work was to validate quantification of signal decrease on high-resolution T(2)-weighted MR sequences before and 24-36 h after USPIO administration for accurate differentiation between benign and malignant normal-sized pelvic lymph nodes. Fifty-eight patients with bladder or prostate cancer were examined on a 3 T MR unit and their respective lymph node signal intensities (SI), signal-to-noise (SNR) and contrast-to-noise (CNR) were determined on pre- and post-contrast 3D T(2)-weighted turbo spin echo (TSE) images. Based on histology and/or localization, USPIO-uptake-related SI/SNR decrease of benign vs malignant and pelvic vs inguinal lymph nodes was compared. Out of 2182 resected lymph nodes 366 were selected for MRI post-processing. Benign pelvic lymph nodes showed a significantly higher SI/SNR decrease compared with malignant nodes (p < 0.0001). Inguinal lymph nodes in comparison to pelvic lymph nodes presented a reduced SI/SNR decrease (p < 0.0001). CNR did not differ significantly between benign and malignant lymph nodes. The receiver operating curve analysis yielded an area under the curve of 0.96, and the point with optimal accuracy was found at a threshold value of 13.5% SNR decrease. Overlap of SI and SNR changes between benign and malignant lymph nodes were attributed to partial voluming, lipomatosis, histiocytosis or focal lymphoreticular hyperplasia. USPIO-enhanced MRI improves the diagnostic ability of lymph node staging in normal-sized lymph nodes, although some overlap of SI/SNR-changes remained. Quantification of USPIO-dependent SNR decrease will enable the validation of this promising technique with the final goal of improving and individualizing patient care.

Ultrasmall superparamagnetic particles of iron oxide allow for the detection of metastases in normal sized pelvic lymph nodes of patients with bladder and/or prostate cancer

Lymph node metastases influence prognosis and outcome in patients with bladder and prostate cancer. Cross sectional imaging criteria are limited in detecting metastases in normal sized lymph nodes. This prospective study assessed the diagnostic accuracy of ultrasmall superparamagnetic particles of iron oxide (USPIO)-enhanced magnetic resonance imaging (MRI) for the detection of metastases in normal sized lymph nodes using extended pelvic lymph node dissection (ePLND) and histopathology as the reference standard.

Influence of preoperative leg pain and radiculopathy on outcomes in mono-segmental lumbar total disc replacement: results from a nationwide registry

Currently, many pre-conditions are regarded as relative or absolute contraindications for lumbar total disc replacement (TDR). Radiculopathy is one among them. In Switzerland it is left to the surgeon's discretion when to operate if he adheres to a list of pre-defined indications. Contraindications, however, are less clearly specified. We hypothesized that, the extent of pre-operative radiculopathy results in different benefits for patients treated with mono-segmental lumbar TDR. We used patient perceived leg pain and its correlation with physician recorded radiculopathy for creating the patient groups to be compared.

From endoplasmic reticulum to secretory granules: role of zinc in the secretory pathway of growth hormone

Endocrine and neuroendocrine cells differ from cells which rapidly release all their secreted proteins in that they store some secretory proteins in concentrated forms in secretory granules to be rapidly released when cells are stimulated. Protein aggregation is considered as the first step in the secretory granule biosynthesis and, at least in the case of prolactin and growth hormone, greatly depends on zinc ions that facilitate this process. Hence, regulation of cellular zinc transport especially that within the regulated secretory pathway is of importance to understand. Various zinc transporters of Slc30a/ZnT and Slc39a/Zip families have been reported to fulfil this role and to participate in fine tuning of zinc transport in and out of the endoplasmic reticulum, Golgi complex and secretory granules, the main cellular compartments of the regulated secretory pathway. In this review, we will focus on the role of zinc in the formation of hormone-containing secretory granules with special emphasis on conditions required for growth hormone dimerization/aggregation. In addition, we highlight the role of zinc transporters that govern the process of zinc homeostasis in the regulated hormone secretion.