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Real-Time Rating of Dynamic Modifications of Anterior Part Biometry as well as Wavefront Aberrations Through Holiday accommodation.
This article is protected by copyright. All rights reserved.Azulene, a unique isomer of naphthalene, has received much interest of researchers from different fields due to its unusual chemical structure with negatively charged 5-membered ring fused with positively charged 7-membered ring. In particular, incorporation of azulene into polymers has led to many interesting properties. This mini-review covers functionalization methods of azulene at its various positions of 5- and 7-membered rings to form azulene derivatives including azulene monomers, and gives an overview of a wide range of azulene-containing polymers including poly(1,3-azulene), azulene-based copolymers with connectivity at 1,3-positions of the 5-membered ring, or 4,7-positions of the 7-membered ring, as well as copolymers with azulene units as side chains. Their chemical and physical properties together with applications of azulene-containing polymers have also been summarized. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.Metalation of anchored porphyrins is essential for their functionality at hybrid interfaces. In this work, we have studied the anchoring and metalation of a functionalized porphyrin derivative, 5-(4-carboxyphenyl)-10,15,20-triphenylporphyrin (MCTPP), on an atomically-defined CoO(100) film under ultrahigh vacuum (UHV) conditions. We follow both the anchoring to the oxide surface and the self-metalation by surface Co 2+ ions via infrared reflection absorption spectroscopy (IRAS). At 150 K, MCTPP multilayer films adsorb molecularly on CoO(100) without anchoring to the surface. Upon heating to 200 K, the first layer of porphyrin molecules anchors via formation of a bridging surface carboxylate. Above 460 K, the MCTPP multilayer desorbs and only the anchored monolayer resides on the surface up to temperatures of 600 K approximately. The orientation of anchored MCTPP depends on the surface coverage. At low coverage, the MCTPP adopts a nearly flat-lying geometry, whereas an upright standing film is formed near the multilayer coverage. Self-metalation of MCTPP depends critically on the surface temperature, the coverage and on the molecular orientation. At 150 K, metalation is largely suppressed, while the degree of metalation increases with increasing temperature and reaches a value of around 60% in the first monolayer at 450 K. At lower coverage higher metalation fractions (85% and above) are observed, similar as for increasing temperature. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.BACKGROUND Percutaneous coronary intervention (PCI) is increasingly utilized for treatment of coronary disease involving the unprotected left main stem (ULMS). However, no studies to date have examined the outcomes of such interventions when complicated by coronary perforation (CP). METHODS Using the British Cardiovascular Intervention society (BCIS) database, data were analyzed on all ULMS-PCI procedures complicated by CP in England and Wales between 2007 and 2014. Multivariate logistic regressions were used to identify predictors of ULMS CP and to evaluate the association between this complication and outcomes. RESULTS During 10,373 ULMS-PCI procedures, CP occurred more frequently than in non-ULMS-PCI (0.9 vs. 0.4%, p  less then  .001) with a stable annual incidence. Covariates associated with CP included number of stents used, female gender, use of rotational atherectomy and chronic total occlusion (CTO) intervention. Adjusted odds of adverse outcomes for ULMS-PCI complicated by CP were higher for peri-procedural complications including cardiogenic shock, tamponade, side-branch loss, DC cardioversion, in-hospital major bleeding, transfusion requirement, and peri-procedural myocardial infarction. There were also significantly increased odds for in-hospital major adverse cardiac events (MACCE, OR 8.961, 95% CI [4.902-16.383]) and 30-day mortality (OR 5.301, 95% CI [2.741-10.251]). CONCLUSIONS CP is an infrequent event during ULMS-PCI and is predicted by female gender, rotational atherectomy, CTO interventions or number of stents used. CP was associated with significantly higher odds of mortality and morbidity, but at rates similar to previously published all-comer PCI complicated by CP. © 2020 Wiley Periodicals, Inc.PURPOSE Hydrogel spacers are a tool to improve dosimetry and overall quality of life in men receiving radiotherapy for prostate cancer. This study is a pooled analysis of a prospective cohort with long-term quality of life (QOL) follow-up data with or without hydrogel spacers to minimize the dose to adjacent organs at risk. METHODS AND MATERIALS QOL was examined using the Expanded Prostate Cancer Index Composite (EPIC) and mean changes from baseline to EPIC domains were evaluated. A total of 215 patients from a randomized multi-institutional trial of radiation with or without hydrogel spacer with a QOL end-point were pooled with 165 non-randomized patients from a single institution with prospective QOL collection in patients with or without hydrogel spacer. The proportions of men with minimally important differences (MIDs) relative to pre-treatment baseline in the bowel domain were tested using repeated measure logistic models with a pre-specified threshold for clinically significant declines (>/= 5 equivalennts (p=0.009). CONCLUSIONS In this pooled analysis of QOL after prostate radiotherapy with up to 5-years of follow-up, utilization of a rectal spacer was associated with preservation of bowel QOL. This QOL benefit was preserved with long-term follow-up. This article is protected by copyright. All rights reserved.The configuration dependent self-association mode of the two anomers of O-Ac,N -Fmoc-D-Glucosamine, a foldamer building block, leading to gel and/or single crystal formation is described. The β-anomer of the sugar amino acid ( 2 ) forms a gel from various solvents (confirmed by SEM, rheology measurements, NMR and ECD spectroscopy), while the α-anomer ( 1 ) forms none of those tested. Transition from solution state to gel is coupled to a concurrent shift of the Fmoc-groups from a freely rotating (almost symmetrical) to a specific, asymmetric orientation. While the crystal structure of the α-anomer is built as an evenly packed 3D-system, the β-anomer forms a looser superstructure of well-packed 2D-layers. Modeling indicates that in the lowest energy, but scarcely sampled conformer of the β-anomer, the Fmoc-group bends above the sugar moiety, stabilized by intramolecular CH↔π interaction between the aromatic rings. We conclude that possessing an extended and promiscuous interaction surface and a conformationally heterogeneous solution state are among the basic requirements of gel formation for a candidate molecule. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.After the first reported case of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) infection in Wuhan, China, in December 2019, the contagion has spread rapidly and has become a global pandemic.1 There are as of yet no published studies beyond the case series describing the incidence and clinical course of COVID-19 in transplant recipients, a population potentially at high risk due to the ongoing immunosuppression and higher risk of comorbidities.2 This pandemic has had a major impact in transplant physicians and healthcare workers as well3 and this crisis has meant reducing or even interrupting transplant program activity, with a subsequent impact on patient morbidity and mortality that is still hard to quantify. This article is protected by copyright. All rights reserved.We report here an operationally very simple method to greatly facilitate chemical protein synthesis by fully convergent and one-pot native chemical ligations utilizing the Fluorenylmethyloxycarbonyl (Fmoc) moiety as an N-masking group of the N-terminal cysteine of the middle peptide thioester segment(s). The Fmoc group is stable to harsh oxidative conditions frequently used to generate peptide thioester from hydrazide or o-aminoanilide. The ready availability of the Fmoc-Cys(Trt)-OH, routinely used in Fmoc chemistry solid phase peptide synthesis, where the Fmoc group is pre-installed on cysteine residue, minimizes additional steps required for the temporary protection of the N-terminal cysteinyl peptides. The Fmoc group is readily removed after ligation reaction by short exposure ( less then 7 min) to 20% piperidine at pH 11 in aqueous condition at room temperature. Subsequent native chemical ligation reactions can be performed in presence of piperidine in the same solution at pH 7. © 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.General Anesthesia (GA) exposure and the potential concern for neurotoxicity in children remains controversial. In 2017, European anesthesia societies emphasized the importance of counseling parents to balance the benefits of elective interventions requiring GA with potential risks of GA exposure. Studies on parental perspectives on the topic in the United States (U.S.) are lacking. We aimed to better understand parental concerns of GA exposure in young children in the U.S. This article is protected by copyright. All rights reserved.Natural killer group 2 member D (NKG2D) ligands (NKG2DLs) on tumor cells engage NKG2D and mediate the killing by NKG2D+ immune cells. However, tumor cells with high NKG2DLs are still malignant and proliferate rapidly. We investigated the reason for NKG2DL-expressing cell progression. Tumor cells in mice were assessed for their NKG2DL expression, ability to attract immune cells, tumorigenicity, mTOR and signal transducer and activator of transcription 3 (STAT3) signaling activation. The antibody blockade was used to determine the effect of NKG2DL-NKG2D interaction on the signaling activation in vitro. Retinoic acid early inducible gene 1 (Rae1) was related to the expression of other NKG2DLs, the promotion of tumorigenicity, Mmp2 expression, mTOR and STAT3 phosphorylation in GL261 cells, and the recruitment of NKG2D+ cells in mice. Rae1 also induced NKG2DL expression, mTOR and STAT3 phosphorylation in GL261 cells and LLC cells but not in B16 and Pan02 cells, which did not express NKG2DLs, when cocultured with PBMCs, and the induced phosphorylation was eliminated by Rae1-NKG2D blockade. The inhibition of mTOR and/or STAT3 decreased the PBMC-induced migration and proliferation of GL261 cells in vitro. Rae1, a NKG2DL on the tumor cells, plays a driving role on other NKG2DL expression and tumor development in mice by activating mTOR and STAT3 pathways relying on its interaction with NKG2D on immune cells. This article is protected by copyright. All rights reserved.Cellular signaling is regulated by assembly of proteins into higher-order complexes. selleckchem Bottom-up creation of synthetic protein assemblies, especially asymmetric complexes, is highly challenging. Here, we present the design and implementation of asymmetric assembly of a ternary protein complex facilitated by Rosetta modeling and thermodynamic analysis. We targeted the wildtype symmetric CT32-CT32 interface of the 14-3-3/CT32 complex, ultimately favoring asymmetric assembly on the 14-3-3 scaffold. Biochemical studies, supported by mass-balance models, allowed for characterization of the parameters driving asymmetric assembly. Importantly, our work reveals that both the individual binding affinities and cooperativity between the assembling components are crucial when designing higher-order protein complexes. Enzyme complementation on the 14-3-3 scaffold highlighted that interface engineering of a symmetric ternary complex generates asymmetric protein complexes with new functions. © 2020 WILEY-VCH Verlag GmbH & Co.
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