Ru-Catalyzed, cis-Selective Living Ring-Opening Metathesis Polymerization of Various Monomers, Including a Dendronized Macromonomer, and Implications to Enhanced Shear Stability

An unsaturated polymer’s cis/trans-olefin content has a significant influence on its properties. For polymers obtained by ring-opening metathesis polymerization (ROMP), the cis/trans-olefin content can be tuned by using specific catalysts. However, cis-selective ROMP has suffered from narrow monomer scope and lack of control over the polymerization (giving polymers with broad molecular weight distributions and prohibiting the synthesis of block copolymers). Herein, we report the versatile cis-selective controlled living ROMP of various endo-tricyclo[4.2.2.0^(2,5)]deca-3,9-diene and various norbornene derivatives using a fast-initiating dithiolate-chelated Ru catalyst. Polymers with cis-olefin content as high as 99% could be obtained with high molecular weight (up to M_n of 105.1 kDa) and narrow dispersity (<1.4). The living nature of the polymerization was also exploited to prepare block copolymers with high cis-olefin content for the first time. Furthermore, owing to the successful control over the stereochemistry and narrow dispersity, we could compare cis- and trans-rich polynorbornene and found the former to have enhanced resistance to shear degradation

Concomitant Carcinoma in situ in Cystectomy Specimens Is Not Associated with Clinical Outcomes after Surgery

Objective: The aim of this study was to externally validate the prognostic value of concomitant urothelial carcinoma in situ (CIS) in radical cystectomy (RC) specimens using a large international cohort of bladder cancer patients. Methods: The records of 3,973 patients treated with RC and bilateral lymphadenectomy for urothelial carcinoma of the bladder (UCB) at nine centers worldwide were reviewed. Surgical specimens were evaluated by a genitourinary pathologist at each center. Uni- and multivariable Cox regression models addressed time to recurrence and cancer-specific mortality after RC. Results: 1,741 (43.8%) patients had concomitant CIS in their RC specimens. Concomitant CIS was more common in organ-confined UCB and was associated with lymphovascular invasion (p < 0.001). Concomitant CIS was not associated with either disease recurrence or cancer-specific death regardless of pathologic stage. The presence of concomitant CIS did not improve the predictive accuracy of standard predictors for either disease recurrence or cancer-specific death in any of the subgroups. Conclusions: We could not confirm the prognostic value of concomitant CIS in RC specimens. This, together with the discrepancy between pathologists in determining the presence of concomitant CIS at the morphologic level, limits the clinical utility of concomitant CIS in RC specimens for clinical decision-making. Copyright (C) 2011 S. Karger AG, Base

The retina visual cycle is driven by cis retinol oxidation in the outer segments of cones

Vertebrate rod and cone photoreceptors require continuous supply of chromophore for regenerating their visual pigments after photoactivation. Cones, which mediate our daytime vision, demand a particularly rapid supply of 11-cis retinal chromophore in order to maintain their function in bright light. An important contribution to this process is thought to be the chromophore precursor 11-cis retinol, which is supplied to cones from Müller cells in the retina and subsequently oxidized to 11-cis retinal as part of the retina visual cycle. However, the molecular identity of the cis retinol oxidase in cones remains unclear. Here, as a first step in characterizing this enzymatic reaction, we sought to determine the subcellular localization of this activity in salamander red cones. We found that the onset of dark adaptation of isolated salamander red cones was substantially faster when exposing directly their outer vs. their inner segment to 9-cis retinol, an analogue of 11-cis retinol. In contrast, this difference was not observed when treating the outer vs. inner segment with 9-cis retinal, a chromophore analogue which can directly support pigment regeneration. These results suggest, surprisingly, that the cis-retinol oxidation occurs in the outer segments of cone photoreceptors. Confirming this notion, pigment regeneration with exogenously added 9-cis retinol was directly observed in the truncated outer segments of cones, but not in rods. We conclude that the enzymatic machinery required for the oxidation of recycled cis retinol as part of the retina visual cycle is present in the outer segments of cones

Evaluating the strategic plans of public libraries : an inspection-based approach

For public libraries, as with most organisations, effective strategic planning is critical to longevity, facilitating cohesive and coordinated responses to ever present and ever changing political, economic, social, and technological (PEST) forces which shape and influence direction. However, strategic planning is widely recognised as a challenging activity, which can be both time consuming and unproductive, and there exists limited guidance regarding how to evaluate documented and disseminated strategic plans, particularly within the not-for-profit sector. In response, this research proposes and tests an inspection-based approach to the evaluation of strategic plans, based upon a rubric specifying the key attributes of each of the core components of a plan, combined with an appropriate assessment scale. The rubric provides a method to identify and assess completeness of strategic plan, extending to qualitative assessment of communication aspects such as specification and terminology, and synergistic aspects such as cohesion and integration. The method is successfully trialled across the devolved Scottish public library sector with the strategic plans of 28 of the 32 regional networks evaluated. 17 of 28 plans (61%) were found to be incomplete and/or to contain contradictory or uncoordinated components, with it recommended that Scottish public libraries improve not only completeness of plans, but also their precision, specificity, explicitness, coordination, and consistency, and overall mapping to library services. Recommendations are made for further widespread application of the rubric

Simple and Honest Confidence Intervals in Nonparametric Regression

We consider the problem of constructing honest confidence intervals (CIs) for a scalar parameter of interest, such as the regression discontinuity parameter, in nonparametric regression based on kernel or local polynomial estimators. To ensure that our CIs are honest, we use critical values that take into account the possible bias of the estimator upon which the CIs are based. We show that this approach leads to CIs that are more efficient than conventional CIs that achieve coverage by undersmoothing or subtracting an estimate of the bias. We give sharp efficiency bounds of using different kernels, and derive the optimal bandwidth for constructing honest CIs. We show that using the bandwidth that minimizes the maximum mean-squared error results in CIs that are nearly efficient and that in this case, the critical value depends only on the rate of convergence. For the common case in which the rate of convergence is $n^{-2/5}$, the appropriate critical value for 95% CIs is 2.18, rather than the usual 1.96 critical value. We illustrate our results in a Monte Carlo analysis and an empirical application.Comment: 46 pages, plus a 54-page supplemental appendi

Halogen bonding stabilizes a cis-azobenzene derivative in the solid state: A crystallographic study

Crystals of trans- and cis-isomers of a fluorinated azobenzene derivative have been prepared and characterized by single-crystal X-ray diffraction. The presence of F atoms on the aromatic core of the azobenzene increases the lifetime of the metastable cis-isomer, allowing single crystals of the cis-azobenzene to be grown. Structural analysis on the cis-azobenzene, complemented with density functional theory calculations, highlights the active role of the halogen-bond contact (N...I synthon) in promoting the stabilization of the cis-isomer. The presence of a long aliphatic chain on the azobenzene unit induces a phase segregation that stabilizes the molecular arrangement for both the trans- and cis-isomers. Due to the rarity of cis-azobenzene crystal structures in the literature, our paper makes a step towards understanding the role of non-covalent interactions in driving the packing of metastable azobenzene isomers. This is expected to be important in the future rational design of solid-state, photoresponsive materials based on halogen bonding. We show by single-crystal X-ray diffraction studies and computational analysis that halogen bonding can stabilize a metastable cis-azobenzene derivative in the solid state

One-pot domino synthesis of polyvicinalamine monomers

On a genere de l'imidazole par une reaction de type domino in situ entre le glyoxal, le formaldehyde et deux unites d'ammoniac aqueux. L'addition de bicarbonate aqueux et d'un anhydride carboxylique ou d'un dicarbonate de dialkyle conduit a la formation de la N,N'-diacyl- ou N,N'-dicarbalkoxy-2-hydroxyimidazoline correspondante. Il s'ensuit une reaction de clivage de cycle de Bamberger qui permet d'isoler facilement le cis-1,2-di(acetamido)ethene, le cis-1,2-di(propylamido)ethene, le cis-1,2-di(ethoxyamido)ethene, le cis-1,2-di(tert-butoxyamido)ethene ou le cis-1,2-di(benzamido)ethene sous la forme de solides. La facilite et la generalite offerte par cette approche monotope implique une voie efficace du point de vue des couts en vue de la synthese de routine de precurseurs d'amines oligo- et polyvicinales

SMSlingshot a shared encounter in urban space

Interaction design is increasingly situated beyond the desktop and demands new approaches, if it is made for Urban Space. Public and semi-public spaces add new challenges in terms of interaction theory, technology and sociology. SMSlingshot is an interactive unban installation (also named a Shared Encounter) and research vehicle that helps to explore these new challenges