bluuebunny/crossref_metadata_2025_split huggingface dataset:
Multipolar Porphyrin‐Triazatruxene Arrays for Two‐Photon Fluorescence Cell Imaging
Authors: Zhang Jinghui , Gong Lei , Zhang Xiaoshuang , Zhu Mengliang , Su Chaorui , Ma Qing , Qi Dongdong , Bian Yongzhong , Du Hongwu , Jiang Jianzhuang 
Published: May 2020

AbstractTwo‐photon excited fluorescent (TPEF) materials are highly desirable for bioimaging applications owing to their unique characteristics of deep‐tissue penetration and high spatiotemporal resolution. Herein, by connecting one, two, or three electron‐deficient zinc porphyrin units to an electron‐rich triazatruxene core via ethynyl π‐bridges, conjugated multipolar molecules TAT‐(ZnP)n (n=1–3) were developed as TPEF materials for cell imaging. The three new dyes present high fluorescence quantum yields (0.40–0.47) and rationally improved two‐photon absorption (TPA) properties. In particular, the peak TPA cross section of TAT‐ZnP (436 GM) is significantly larger than that of the ZnP reference (59 GM). The δTPA values of TAT‐(ZnP)2 and TAT‐(ZnP)3 further increase to 1031 and up to 1496 GM, respectively, indicating the effect of incorporated ZnP units on the TPA properties. The substantial improvement of the TPEF properties is attributed to the formation of π‐conjugated quadrapole/octupole molecules and the extension of D‐π‐A‐D systems, which has been rationalized by density function theory (DFT) calculations. Moreover, all of the three new dyes display good biocompatibility and preferential targeting ability toward cytomembrane, thus can be superior candidates for TPEF imaging of living cells. Overall, this work demonstrated a promising strategy for the development of porphyrin‐based TPEF materials by the construction and extension of D‐π‐A‐D multipolar array.
Recent Advances in Iodine‐Promoted C−S/N−S Bonds Formation
Authors: Zhang Honghua , Wang Huihong , Jiang Yi , Cao Fei , Gao Weiwei , Zhu Longqing , Yang Yuhang , Wang Xiaodong , Wang Yongqiang , Chen Jinhong , Feng Yiyue , Deng Xuemei , Lu Yingmei , Hu Xiaoling , Li Xiangxiang , Zhang Juan , Shi Tao , Wang Zhen 
Published: May 2020

AbstractSulfur‐containing scaffold, as a ubiquitous structural motif, has been frequently used in natural products, bioactive chemicals and pharmaceuticals, particularly C−S/N−S bonds are indispensable in many biological important compounds and pharmaceuticals. Development of mild and general methods for C−S/N−S bonds formation has great significance in modern research. Iodine and its derivatives have been recognized as inexpensive, environmentally benign and easy‐handled catalysts or reagents to promote the construction of C−S/N−S bonds under mild reaction conditions, with good regioselectivities and broad substrate scope. Especially based on this, several new strategies, such as oxidation relay strategy, have been greatly developed and accelerated the advancement of this field. This review focuses on recent advances in iodine and its derivatives promoted hybridized C−S/N−S bonds formation. The features and mechanisms of corresponding reactions are summarized and the results of some cases are compared with those of previous reports. In addition, the future of this domain is discussed.
A New Class of C2‐Symmetric Chiral Cyclopentadienyl Ligand Derived from Ferrocene Scaffold: Design, Synthesis and Application
Authors: Liang Hao , Vasamsetty Laxmaiah , Li Teng , Jiang Jijun , Pang Xingying , Wang Jun 
Published: May 2020

AbstractA new class of C2‐symmetric, chiral cyclopentadienyl ligand based on planar chiral ferrocene backbone was developed. A series of its corresponding rhodium(I), iridium(I), and ruthenium(II) complexes were prepared as well. In addition, the rhodium(I) complexes were evaluated in the asymmetric catalytic intramolecular amidoarylation of olefin‐tethered benzamides via C−H activation.
Unusual Structures of the Parent Molecules Diarsene, Distibene, and Dibismuthene: Toward Their Observation
Authors: Li Guoliang , Huang Chunxiang , Xie Yaoming , Robinson Gregory H. , Schaefer Henry F. 
Published: May 2020

AbstractThere is considerable interest, from both experimental and theoretical perspectives, in molecules incorporating multiple bonds between main group elements. Herein, we not only consider the parent molecules HE=EH (E=As, Sb, Bi), but also a number of their isomers. For each E2H2 molecule, a number of different structures were optimized with four different DFT methods. Final structures were determined with the coupled cluster method CCSD(T) using large basis sets, namely cc‐pVQZ‐PP, incorporating relativistic psuedopotentials. All feasible dissociation pathways are examined. For all three E2H2 molecules the trans isomer lies lowest in energy, with the cis isomer higher by 2.7 (As), 2.1 (Sb), and 1.8 (Bi) kcal mol−1, respectively. However, both cis and trans structures should be observable, as large barriers (27.7, 20.5, and 17.7 kcal mol−1) separate them. For both the cis and trans structures, in the infrared the strong E‐H stretching frequencies should also be observable. Only the cis structures have dipole moments (0.62, 0.01, and 0.83 debye, respectively), and their observation by microwave spectroscopy would be stunning. Also considered were the higher energy vinylidene‐like, pyramidal, monobridged, and linear structures. We conclude that molecules such as HSb=SbH‐Fe(CO)4, HBi=BiH‐Fe(CO)4, and related systems, should be feasible synthetic targets.
Recycling of Flexible Polyurethane Foam by Split‐Phase Alcoholysis: Identification of Additives and Alcoholyzing Agents to Reach Higher Efficiencies
Authors: Vanbergen Thomas , Verlent Isabel , De Geeter Joke , Haelterman Bart , Claes Laurens , De Vos Dirk 
Published: May 2020

AbstractSplit‐phase alcoholysis of flexible polyurethane (PU) foam yields an apolar phase containing the recycled polyether polyol, and a lower, polar phase of the alcoholyzing agent and aromatic compounds. However, multiple purification steps are required to render the polyether polyol suitable for synthesis of new flexible PU foams; the unfavorable mass balance limits industrial applications. In this work, 2‐pyrrolidone was identified as a performant additive for accelerating the dissolution and depolymerization process. By applying a lactam to PU foam in a weight ratio of 0.1:1, the glycol to PU foam weight ratio can be decreased from 1.5:1 to only 0.5:1, without loss of purity or yield of the recycled polyether polyol. Diglycerol was discovered as a novel, promising alcoholyzing agent; it allows the recycling of the polyether polyol in high purity (97 %) and excellent yields (98 %), and after a single washing with diglycerol, a sufficiently low hydroxyl value (61 mgKOH g−1) is reached. The recycled polyether polyol can replace the virgin polyether polyol (48 mgKOH g−1) for up to 50 % in the synthesis of new flexible PU foams with effects on the foam quality that stay within the limits of generally accepted specifications. A first step towards the valorization of the lower phase was also taken by applying hydrolysis of the newly formed carbamates to toluenediamines, which are readily reintegrated in new PU foams.
Rationale and study design of OUTSTEP‐HF: a randomised controlled study to assess the effect of sacubitril/valsartan and enalapril on physical activity measured by accelerometry in patients with heart failure with reduced ejection fraction
Authors: Edelmann Frank , Jaarsma Tiny , Comin‐Colet Josep , Schorr Jessica , Ecochard Laurent , Hussain Rizwan I. , Piepoli Massimo F. 
Published: May 2020

AbstractAimIn PARADIGM‐HF, sacubitril/valsartan demonstrated superiority to enalapril in reducing mortality and morbidity in patients with heart failure (HF) with reduced ejection fraction (HFrEF). Several patient‐centred outcomes like improved physical activity and quality of life have been emphasised as important treatment goals in HF management. OUTSTEP‐HF has been designed to evaluate the effect of sacubitril/valsartan compared with enalapril on non‐sedentary daytime physical activity in patients with HFrEF.MethodsOUTSTEP‐HF is a randomised, actively controlled, double‐blind, double‐dummy study that plans to enrol 600 ambulatory patients with symptomatic HFrEF in 19 European countries. Patients will be randomised 1:1 to receive sacubitril/valsartan 97/103 mg bid or enalapril 10 mg bid. The primary objective of the study is to assess changes from baseline (Week 0) to Week 12 in exercise capacity measured by the 6‐min walk test and in daily non‐sedentary daytime activity. Physical activity and objective sleep parameters will be measured by accelerometry using a wrist‐worn device, worn continuously from screening (Week −2) until the end of study (Week 12). As a co‐primary outcome, changes from baseline in sub‐maximal exercise capacity will be assessed by the 6‐min walk test. Patient‐ and physician‐reported questionnaires will be used to assess quality of life, changes in signs and symptoms of HF and sleep parameters.ConclusionOUTSTEP‐HF will be the largest randomised trial in HF to date to use non‐invasive accelerometry to assess whether treatment with sacubitril/valsartan improves patients' daily physical activity and exercise capacity compared with enalapril.
Biogeomorphology in the marine landscape: Modelling the feedbacks between patches of the polychaete worm Lanice conchilega and tidal sand waves
Authors: Damveld Johan H. , Borsje Bas W. , Roos Pieter C. , Hulscher Suzanne J. M. H. 
Published: May 2020

AbstractTidal sand waves are dynamic bedforms found in coastal shelf seas. Moreover, these areas are inhabited by numerous benthic species, of which the spatial distribution is linked to the morphological structure of sand waves. In particular, the tube‐building worm Lanice conchilegais of interest as this organism forms small mounds on the seabed, which provide shelter to other organisms. We investigate how the interactions between small‐scale mounds (height ∼dm) and large‐scale sand waves (height ∼m) shape the bed of the marine environment. To this end, we present a two‐way coupled process‐based model of sand waves and tube‐building worm patches in Delft3D. The population density evolves according to a general law of logistic growth, with the bed shear stress controlling the carrying capacity. Worm patches are randomly seeded and the tubes are mimicked by small cylinders that influence flow and turbulence, thereby altering sediment dynamics. Model results relate the patches with the highest worm densities to the sand wave troughs, which qualitatively agrees with field observations. Furthermore, the L. conchilegatubes trigger the formation of sandy mounds on the seabed. Because of the population density distribution, the mounds in the troughs can be several centimetres higher than on the crests. Regarding sand wave morphology, the combination of patches and mounds are found to shorten the time‐to‐equilibrium. Also, if the initial bed comprised small sinusoidal sand waves, the equilibrium wave height decreased with a few decimetres compared to the situation without worm patches. As the timescale of mound formation (years) is shorter than that of sand wave evolution (decades), the mounds induce (and accelerate) sand wave growth on a similar spatial scale to the mounds. Initially, this leads to shorter sand waves than they would be in an abiotic environment. However, near equilibrium the wavelengths tend towards their abiotic counterparts again. © 2020 The Authors. Earth Surface Processes and Landforms published by John Wiley & Sons Ltd
Modelling the impact of a time‐varying wave angle on the nonlinear evolution of sand bars in the surf zone
Authors: Nnafie Abdel , van Andel Niek , de Swart Huib 
Published: May 2020

ABSTRACTSandy beaches are often characterized by the presence of sand bars, whose characteristics (growth, migration speed, etc.) strongly depend on offshore wave conditions, such as wave height and angle of wave incidence. This study addresses the impact of a sinusoidally time‐varying wave angle of incidence with different time‐means on the saturation height, migration speed and longshore spacing of sand bars. Model results show that shore‐transverse sand bars (so‐called TBR bars) eventually develop under a time‐varying wave angle. Depending on the time‐mean, amplitude and period of the varying angle of wave incidence, the mean heights and mean migration speeds of the bars can be larger or smaller than their corresponding values in the case of time‐invariant angles. Bars might not even form when the wave angle varies around a too large oblique mean value, whereas bars exist in the case of a time‐invariant wave angle. The oscillations in both bar height and migration speed are large if the period of the time‐varying wave angle is close to the adjustment timescale of the system and if large differences in the local growth and migration rates of the bars occur during one oscillation period. The oscillations in bar height are a combination of harmonics with the principal period and half the period of the time‐varying wave angle, whereas those of migration speed contain only the principal period. Bars that are subject to time‐varying wave angles have larger longshore crest‐to‐crest spacings than those which form under fixed wave angles. Physical explanations for these findings are given. © 2020 The Authors. Earth Surface Processes and Landforms published by John Wiley & Sons Ltd
Prognostic impact of B‐vitamins involved in one‐carbon metabolism in patients with diffuse large B‐cell lymphoma
Authors: Cao Yiwen , Chen Peizhan , Cai Minci , Shi Qing , Xu Pengpeng , Wang Li , He Yang , Wang Hui , Zhao Weili 
Published: May 2020

AbstractOne‐carbon metabolism (OCM) plays a pivotal role in both the stability and integrity of DNA and is mainly regulated by B‐vitamins. This study aims to investigate the clinical relevance of B‐vitamins and single nucleotide polymorphisms (SNPs) on OCM‐related genes in diffuse large B‐cell lymphoma (DLBCL). A total of 322 newly diagnosed DLBCL patients who received rituximab plus cyclophosphamide, doxorubicin, vincristine, and prednisone‐based immunochemotherapy were recruited into this study. The serum levels of B‐vitamins (folate, vitamin B2 [riboflavin], vitamin B6 [pyridoxal 5′‐phosphate], and vitamin B12 [cobalamin]), as well as SNPs on methylenetetrahydrofolate reductase, methionine synthase (MTR), MTR reductase (MTRR) and cystathionine gamma‐lyase (CTH) genes, were assessed at diagnosis. The prognostic values were estimated using the Kaplan‐Meier method and Cox proportional hazards regression methods. Overall, the low serum concentration of folate and vitamin B2, as well as the presence of CTH1364 TT genotype, were significantly associated with poor treatment response in DLBCL. Multivariate analysis indicated that compared with patients in the medium and high serum folate tertiles, low serum folate tertile patients had both significantly inferior progression‐free survival (P = .033, Tertile 2 vs Tertile 1, and P = .031, Tertile 3 vs Tertile 1) and overall survival time (P < .001, Tertile 2 vs Tertile 1, and P = .001, Tertile 3 vs Tertile 1). Compared with patients in the medium and high serum vitamin B2 tertiles, low serum vitamin B2 tertile patients had both significantly inferior progression‐free survival (P = .006, Tertile 2 vs Tertile 1, and P = .001, Tertile 3 vs Tertile 1) and overall survival time (P = .030, Tertile 2 vs Tertile 1, and P = .255, Tertile 3 vs Tertile 1). In conclusion, alterations in B‐vitamin metabolism significantly affected disease progression and had a prognostic impact on DLBCL.
The role of snow processes and hillslopes on runoff generation in present and future climates in a recently constructed watershed in the Athabasca oil sands region
Authors: Biagi Kelly M. , Carey Sean K. 
Published: May 2020

AbstractMine reclamation in the Athabasca oil sands region Canada, is required by law where companies must reconstruct disturbed landscapes into functioning ecosystems such as forests, wetlands, and lakes that existed in the Boreal landscape prior to mining. Winter is a major hydrological factor in this region as snow covers the landscape for 5–6 months and is ~25% of the annual precipitation, yet few studies have explored the influence of winter processes on the hydrology of constructed watersheds. One year (2017–2018) of intensive snow hydrology measurements are supplemented with 6 years (2013–2018) of meteorological measurements from the constructed Sandhill Fen watershed to: (a) understand snow accumulation and redistribution, snowmelt timing, rate, and partitioning, (b) apply a physically based model for simulating winter processes on hillslopes, and (c) evaluate the impact of soil prescriptions and climate change projections on winter processes in reclaimed systems. The 2017–2018 snow season was between November and April and snow water equivalent (SWE) ranged between 40 and 140 mm. Snow distribution was primarily influenced by topography with little influence of snow trapping from developing vegetation. Snow accumulation was most variable on hillslopes and redistribution was driven by slope position, with SWE greatest at the base of slopes and decreased toward crests. Snowmelt on hillslopes was controlled by slope aspect, as snow declined rapidly on west and south‐facing slopes, compared with east and north‐facing slopes. Unlike results previously reported on constructed uplands, snowmelt runoff from uplands was much less (~30%), highlighting the influence of different construction materials. Model simulations indicate that antecedent soil moisture and soil temperature have a large influence on partitioning snowmelt over a range of observed conditions. Under a warmer and wetter climate, average annual peak SWE, and snow season duration could decline up to 52% and up to 61 days, respectively, while snowmelt runoff ceases completely under the warmest scenarios. Results suggest considerable future variability in snowmelt runoff from hillslopes, yet soil properties can be used to enhance vertical or lateral flows.
Decreased numbers of metachromatic cells in nasal swabs in Japanese cedar pollinosis following sublingual immunotherapy
Authors: Otsuka Kuninori , Otsuka Hirokuni , Matsune Shoji , Okubo Kimihiro 
Published: May 2020

AbstractBackground and ObjectiveNasal symptoms were reduced following allergen‐specific sublingual immunotherapy (SLIT) for allergic rhinitis. The mechanisms underlying the effectiveness of SLIT for Japanese cedar pollinosis are poorly understood. We studied changes in the numbers of metachromatic cells, eosinophils, and neutrophils following SLIT for Japanese cedar pollinosis.MethodsNasal swabs were taken in the preseason (n = 32) and in pollinosis season (n = 49) from subjects given sublingual drop immunotherapy for an average duration of 1.5 years. The numbers of metachromatic cells (mast cells and basophils), eosinophils and neutrophils were determined and compared with those from untreated subjects in preseason (n = 65) and in season (n = 54).ResultsSLIT subjects had a significantly reduced frequency of moderate to most severe symptoms in comparison to untreated subjects in preseason (P < .001, the Mann‐Whitney U test), and (P < .00001) in season. Metachromatic cell counts in nasal swabs of SLIT subjects in preseason and in season were lower than those of untreated subjects (P = .014, the Mann‐Whitney U test) and (P = .00001) respectively. Eosinophil numbers in SLIT subjects were not significantly different than in untreated subjects in both preseason (P = .29) and in season (P = .09). However, when SLIT subjects in season were divided into those with greater than or equal to 1.5 years, or <1.5 years of SLIT duration, the degree of eosinophilia in those with SLIT greater than or equal to 1.5 years was significantly lower (P = .011) than in untreated patients, but not in those with SLIT less than 1.5 years (P = .9). There were no significant differences in neutrophil numbers in nasal swabs between untreated and SLIT subjects in preseason and in season.ConclusionOne of mechanisms underlying the effectiveness of sublingual drop immunotherapy for Japanese cedar pollinosis is a reduction of the number of metachromatic cells in preseason and in season. Eosinophilia was also reduced in season in those given SLIT for greater than or equal to 1.5 years.
Molecular characterisation of TP53 mutated squamous cell carcinomas of the lung to identify putative targets for therapy
Authors: Haakensen Vilde D. , Khadse Anand , Sandhu Vandana , Halvorsen Ann Rita , Solberg Steinar K. , Jørgensen Lars H. , Brustugun Odd Terje , Kure Elin H. , Helland Åslaug 
Published: May 2020

AbstractPersonalised cancer treatment depends on identification of therapeutically relevant biological subgroups of patients for assessing effect of treatment and to discover new therapeutic options. By analyses in heterogeneous patient populations, the effects may be lost in noise. Squamous cell carcinoma of the lung is a major killer worldwide. Despite recent advances, mortality is high and response to therapies varies greatly from patient to patient. Target search in biologically relevant subgroups may identify treatment options not so far discovered. A total of 198 patients undergoing surgery for squamous cell carcinomas of the lung were included in the study. The tumours were analysed for copy number alterations (n = 152) and gene expression from tumour (n = 188) and normal lung (n = 21), with both data levels present in 140 patients. We studied alterations in tumours harbouring mutations in TP53 and in previously published gene expression subtypes. Genes with consistent alterations in both genomic levels were identified as putative biomarkers. Results were validated in TCGA. The most convincing biomarker in TP53 mutated squamous cell carcinomas of the lung was BIRC5 with amplification in 36% of mutated samples, 5% in wild‐type samples and a 17%‐fold change of expression between TP53 mutated tumours and normal lung tissue. BIRC5 was significantly altered in the classical and primitive subtypes. We suggest BIRC5 as a putative predictive biomarker and putative druggable target in squamous cell lung carcinomas harbouring TP53 mutation or classified as classical and primitive subtypes.
The impact of high‐fidelity simulation on knowledge, critical thinking, and clinical decision‐making for the management of pre‐eclampsia
Authors: Akalin Ayse , Sahin Sevil 
Published: May 2020

AbstractObjectiveTo investigate the impact of high‐fidelity simulation on nursing students’ knowledge, critical thinking, and clinical decision‐making in the management of pre‐eclampsia, and to explore the students’ views and learning experiences.MethodsA mixed‐methods design study was conducted on 107 third‐year nursing students. The students were randomly assigned to the control group (n=54) or the experimental group (n=53). The students in the experimental group attended the simulation training using a high‐fidelity simulator, while the students in the control group attended only the classical training on “the management of pre‐eclampsia.”ResultsKnowledge (P<0.001), critical thinking (P<0.05), and clinical decision‐making (P<0.05) scores of students in the experimental group increased after the simulation. In the focus group interviews, five themes were identified: learning development; closing the gap between theory and practice; confident decision‐making and self‐confidence; professional preparation; and recommendations.ConclusionHigh‐fidelity simulation is efficacious for improving the management of pre‐eclampsia among nursing students.