bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Ligand‐Enabled Palladium‐Catalyzed Highly para‐Selective Difluoromethylation of Aromatic Ketones
Authors: Tu Guangliang , Yuan Chunchen , Li Yuting , Zhang Jingyu , Zhao Yingsheng 
Published: October 2018

AbstractA practical and highly para‐selective C−H difluoromethylation of aromatic ketones has been developed by employing tetrakis(triphenylphosphine)palladium(0) as the catalyst and triphenylphosphine as the ligand. In addition to general aromatic ketones, this transformation was compatible with bioactive compounds and well‐known drugs, such as oxybenzone, ketoprofen, zaltoprofen, and propafenone. Moreover, a mechanistic study revealed that a palladium intermediate coordinated by a carbonyl group promotes highly para‐selective difluoromethylation.
Terraced and Smooth Gradient Polymer Brushes via a Polymer Single‐Crystal Assisted Grafting‐To Method
Authors: Mei Shan , Li Christopher Y. 
Published: October 2018

AbstractGradient polymer brushes provide a spatial gradient change in molecular characteristics of the brush, and such a change can be utilized to study structure–property relationships in a combinatorial fashion. In this study, a bottom‐up method was used to synthesize gradient polymer brushes with a predesigned and precisely controlled grafting density gradient and brush pattern. A polymer single‐crystal assisted grafting‐to (PSCAGT) method was employed where end‐functionalized polymers were grown into two‐dimensional polymer single crystals. The latter were chemically coupled to a solid substrate to form well‐defined polymer brushes. To tune the grafting density, end‐dissimilar polymers were used to co‐crystallize into one single crystal. Programmed single‐crystal growth was introduced to synthesize brushes with two different gradient architectures, that is, terraced and smooth gradient with pyramid patterns. This work demonstrates that the PSCAGT method offers a unique means to tune polymer brush nanostructure.
Structural characterizations, spectroscopic, electrochemical properties, and antibacterial activities of copper (II) and cobalt (II) complexes containing imidazole ring
Authors: Chai Lan‐Qin , Zhou Ling , Zhang Kong‐Yan , Zhang Hong‐Song 
Published: October 2018

Two two‐dimensional and three‐dimensional supramolecular complexes [M (L)2] (NO3)2·2CH3OH (M = Cu(1) and Co(2), L = 2‐(4‐imidazolyl)‐4‐methyl‐1,2‐quinazoline‐N3‐oxide), were synthesized and characterized by FT‐IR and UV–Vis spectroscopy, as well as elemental analysis. The spectroscopic data of both complexes were compared with the ligand L. Both complexes were determined by X‐ray single‐crystal diffraction and display similar coordination geometry and have a 2:1 ligand‐to‐metal ratio. All the central M (II) atoms are hexa‐coordinated with perfect octahedral geometries. In the crystal structures, complexes 1 and 2 form an infinite 1‐D chain‐like and 2‐D, 3‐D supramolecular frameworks. X‐ray photoelectron spectrum (XPS) and thermal stability of 2 was investigated. Moreover, electrochemical properties and antimicrobial activities of both complexes were also studied.
A novel purine derivative‐based colorimetric chemosensor for sequential detection of copper ion and sulfide anion
Authors: Jin Xinxin , Chen Huilian , Zhang Weixia , Wang Biyi , Shen Wei , Lu Hongfei 
Published: October 2018

A purine derivative‐based colorimetric chemosensor (PHP) for the detection of Cu2+ and S2− is reported. PHP demonstrated a high selectivity and sensitivity for Cu2+ through color change from colorless to yellow with a detection limit of 74.9 nM. The sensing mechanism of the PHP–Cu complex was confirmed using X‐ray crystal structure analysis and density functional theory calculation. Furthermore, the PHP–Cu complex can be used for selective detection of S2− via competitive complexation of S2− to Cu2+. Finally, PHP was successfully applied as a visible test strip for the detection of cupric ions in water.
Model‐assisted process characterization and validation for a continuous two‐column protein A capture process
Authors: Baur Daniel , Angelo James , Chollangi Srinivas , Müller‐Späth Thomas , Xu Xuankuo , Ghose Sanchayita , Li Zheng Jian , Morbidelli Massimo 
Published: October 2018

AbstractIn this study we introduce three process characterization approaches toward validation of continuous twin‐column capture chromatography (CaptureSMB), referred to as “standard,” “model assisted,” and “hybrid.” They are all based on a traditional risk‐based approach, using process description, risk analysis, design‐of‐experiments (DoE), and statistical analysis as essential elements. The first approach, the “standard” approach uses a traditional experimental DoE to explore the design space of the high‐ranked process parameters for the continuous process. Due to the larger number of process parameters in the continuous process, the DoE is extensive and includes a larger number of experiments than an equivalent DoE of a single column batch capture process. In the investigated case, many of the operating conditions were practically infeasible, indicating that the design space boundaries had been chosen inappropriately. To reduce experimental burden and at the same time enhance process understanding, an alternative “model assisted” approach was developed in parallel, employing a chromatographic process model to substitute experimental runs by computer simulations. Using the “model assisted” approach only experimental conditions that were feasible in terms of process yield constraints (>90%) were considered for statistical analysis. The “model assisted” approach included an optimization part that identified potential boundaries of the design space automatically. In summary, the “model assisted” approach contributed to increased process understanding compared to the “standard” approach. In this study, a “hybrid” approach was also used containing the general concepts of the “standard” approach but substituting a number of its experiments by computer simulations. The presented approaches contain essential elements of the Food and Drug Administration’s process validation guideline.
Long‐term clinical outcome of persistent left bundle branch block after transfemoral aortic valve implantation
Authors: Keßler Mirjam , Gonska Birgid , Seeger Julia , Rottbauer Wolfgang , Wöhrle Jochen 
Published: October 2018

AbstractObjectiveThe impact of persistent left bundle‐branch block (pLBBB) on long‐term clinical outcome remains to be determined.BackgroundNew‐onset of pLBBB occurs frequently after transfemoral aortic valve implantation (TAVI).MethodsSeven hundred and seven consecutive patients who underwent TAVI were analyzed for baseline and procedural characteristics and clinical outcome in an up to 2‐year follow‐up. Patients were divided into either a group with pLBBB until hospital discharge or a group without LBBB. We performed propensity‐score matching and analyzed baseline characteristics, procedural data and clinical outcome of both groups. Patients received balloon‐expandable valves in 56.4%, mechanically expandable valves in 37.5%, and self‐expandable valves in 6.3%.ResultsA new‐onset, pLBBB was observed in 47.5% of patients after TAVI. The implantation of a mechanically expandable valve was associated with higher rate of pLBBB (54.2% vs. 20.8%, P < 0.001), whereas implantation of a balloon‐expandable valve was associated with lower incidence of pLBBB (39.8% vs. 73.1%, P < 0.001). Deeper ventricular implantation at left‐coronary side led to higher rates of pLBBB (7.5 ± 2.5 vs. 6.7 ± 2.6 mm, P < 0.001). The occurrence of pLBBB was associated with higher rates of permanent pacemaker implantation (40.9% vs. 15.9%, P < 0.001). By multivariate analysis, implantation of a mechanically expandable valve (Boston Scientific Lotus valve) was identified as independent predictor of occurrence of pLBBB (odds ratio 4.7, confidence interval 3.2–7.0, P < 0.001). In the 2‐year follow‐up, there were no significant differences between “pLBBB” and “no LBBB”—groups regarding mortality and rehospitalization due to heart failure.ConclusionsThe occurrence of pLBBB is associated with the choice of valve type and implantation depth and requires significantly higher rates of permanent pacemaker implantations. Importantly, there are no differences in the 2‐year follow‐up regarding mortality and rehospitalization due to heart failure.
Mechanistic Insights into Manganese (I)‐Catalyzed Chemoselective Hydroarylations of Alkynes: A Theoretical Study
Authors: Wang Zheyuan , Zhu Lei , Zhong Kangbao , Qu Ling‐Bo , Bai Ruopeng , Lan Yu 
Published: October 2018

AbstractDensity functional theory calculations were employed to elucidate the mechanism of Mn‐catalyzed chemoselective hydroarylation reactions. The Mn‐catalyzed [4+2] annulation undergoes a reaction pathway involving sequential imine‐directed C−H bond cleavage, alkyne insertion into the Mn−C bond, β‐oxygen elimination and outer catalytic cycle annulation–aromatization. Computational results demonstrated that the previously proposed chelation‐assisted alkyne insertion process was unfavorable owing to the weak coordination ability of the β‐oxygen leaving group compared with that of CO. Further noncovalent interactions analysis indicated that the origin of the high regioselectivity was contributed to the steric repulsion resulting from significant nonbonding overlap between the reacting aryl moiety and the quaternary carbon group of the reactant in the alkyne insertion step. In addition, in the Brønsted‐acid‐mediated chemoselective alkenylation reaction, the used terminal alkynes had relatively enhanced reactivity in the alkyne insertion step owing to its reduced steric repulsion. From the active alkenyl‐Mn intermediate, the activation free energy of protonation and β‐oxygen elimination are approximate, thus the alkenylated product is obtained after protonation in an acidic system. We expect that this detailed mechanistic study will significantly enhance our ability to develop Mn‐catalyzed arene C−H bond functionalization reactions.
Evaluating the effectiveness of conservation measures for European grassland‐breeding waders
Authors: Franks Samantha E. , Roodbergen Maja , Teunissen Wolf , Carrington Cotton Anne , Pearce‐Higgins James W. 
Published: October 2018

AbstractFarmland birds are among the most threatened bird species in Europe, largely as a result of agricultural intensification which has driven widespread biodiversity losses. Breeding waders associated with grassland and arable habitats are particularly vulnerable and a frequent focus of agri‐environment schemes (AES) designed to halt and reverse population declines. We review existing literature, providing a quantitative assessment of the effectiveness of policy and management interventions used throughout Europe to improve population and demographic metrics of grassland‐breeding waders. Targeted AES and site protection measures were more likely to be effective than less targeted AES and were ten times more likely to be effective than would be expected by chance, particularly for population trend and productivity metrics. Positive effects of AES and site protection did not appear synergistic. Management interventions which had the greatest chance of increasing population growth or productivity included modification of mowing regimes, increasing wet conditions, and the use of nest protection. Success rates varied according to the species and metric being evaluated. None of the policy or management interventions we evaluated were associated with a significant risk of negative impacts on breeding waders. Our findings support the use of agri‐environment schemes, site protection, and management measures for grassland‐breeding wader conservation in Europe. Due to publication bias, our findings are most applicable to intensively managed agricultural landscapes. More studies are needed to identify measures that increase chick survival. Despite broadly effective conservation measures already in use, grassland‐breeding waders in Europe continue to decline. More research is needed to improve the likelihood and magnitude of positive outcomes, coupled with wider implementation of effective measures to substantially increase favorable land management for these species.
Age and stand structure of oak woodlands along a gradient of conifer encroachment in northwestern California
Authors: Schriver Madelinn , Sherriff Rosemary L. , Varner J. Morgan , Quinn‐Davidson Lenya , Valachovic Yana 
Published: October 2018

AbstractMany fire‐maintained savannas and woodlands are suffering the effects of fire exclusion and the concomitant invasion of fire‐sensitive trees. In the Pacific West, woodlands dominated by either Oregon white oak (Quercus garryana) or California black oak (Quercus kelloggii) have transitioned from oak‐dominated to conifer‐dominated (primarily by the native Douglas‐fir;Pseudotsuga menziesii) forest conditions with corresponding losses of plant and animal biodiversity. In spite of the prevalence of this transition, few studies have documented these temporal shifts and the consequences for oak woodland ecosystems. To better understand this process, we assessed tree species composition and age structure across 10 sites in northwestern California,USA. Species composition varied, but Douglas‐fir, Oregon white oak, and California black oak had the greatest proportional dominance within and across sites. Across all ten sites, we cored 1747 trees from 10 different species. The majority (>80%) of oak stems dated between 1850 and 1910 (69% plots dated within a 40‐yr period from 1860 to 1900). Less than 1% of the oak stems originated after 1960. Across the gradient of encroachment (i.e., oak to conifer dominance) at each site, the most common encroaching species was Douglas‐fir, which primarily established after 1970 (73% across all sites). Douglas‐fir structural attributes were not associated with any of the abiotic factors evaluated, although non‐significant trends show greater densities of Douglas‐fir in oak stands at the northern end of the study region. Oak seedlings were common in all 10 study sites; however, we documented very few oak saplings regardless of the biophysical conditions. This study highlights that (1) the process and severity of encroachment is consistent across the region, resulting in substantial oak habitat loss and a shift toward conifer dominance and vegetative homogeneity in formerly diverse woodlands of northwestern California; and (2) Oregon white oak and California black oak woodlands require concerted management effort to ensure their survival and future persistence.
Decadal effects of thinning on understory light environments and plant community structure in a subtropical forest
Authors: Tsai Ho‐Chen , Chiang Jyh‐Min , McEwan Ryan W. , Lin Teng‐Chiu 
Published: October 2018

AbstractCanopy‐opening disturbance such as thinning has immediate and substantive effects on understory microclimate and therefore the establishment and growth of understory plants. A large number of studies have reported the effects of thinning on tree growth, but few studies have examined long‐term effects of thinning on understory light environments and species and functional diversity of understory plants. Even less is known whether the change in understory plant community structure observed following canopy disturbance is short‐lived and would diminish as the canopy closes or a long lasting due to legacy effects. We examined the effects of an experimental removal of 25% and 50% of the woody vegetation on understory light availability and variability on understory plant community structure in a subtropical Cryptomeria japonica plantation nine years after the treatment. Differences in availability of understory light among treatments diminished nine years after the experimental vegetation removal (thinning), but variability of understory light was still two times higher in the thinned treatments than the un‐thinned control. Species diversity of dominant and common understory plants was lower in the control than in the two thinning treatments, which were not different from each other. Community species and functional composition were also different between the un‐thinned control and the two thinning treatments. The thinned plots had proportionally more individuals of grasses and forbs and fewer individuals of ferns. Our results indicate that the effects of thinning on understory light variability last longer than on light availability representing an important and long‐lasting alteration of resource heterogeneity. At both species and functional group levels, greater diversity and unique composition in the thinned treatments compared to undisturbed control suggest a link between resource heterogeneity and biodiversity in the forest understory or legacy effects associated with the thinning‐induced changes in understory plant community.
TGF‐β suppresses RasGRP1 expression and supports regulatory T cell resistance against p53‐induced CD28‐dependent T‐cell apoptosis
Authors: Takami Mariko , Cunha Christina , Motohashi Shinichiro , Nakayama Toshinori , Iwashima Makio 
Published: October 2018

AbstractThymus‐derived regulatory T cells (tTregs) play pivotal roles in immunological self‐tolerance and homeostasis. A majority of tTregs are reactive to self‐antigens and are constantly exposed to antigenic stimulation. Despite this continuous stimulation, tTreg and conventional T‐cell populations remain balanced during homeostasis, but the mechanisms controlling this balance are unknown. We previously reported a form of activation‐induced cell death, which is dependent on p53 (p53‐induced CD28‐dependent T‐cell apoptosis, PICA). Under PICA‐inducing conditions, tTregs survive while a majority of conventional T cells undergo apoptosis, suggesting there is a survival mechanism that protects tTregs. Here, we report that the expression of RasGRP1 (Ras guanyl‐releasing protein 1) is required for PICA, as conventional T cells isolated from RasGRP1‐deficient mice become resistant to PICA. After continuous stimulation, tTregs express a substantially lower amount of RasGRP1 compared to conventional T cells. This reduced expression of RasGRP1 is dependent on TGF‐β, as addition of TGF‐β to conventional T cells reduces RasGRP1 expression. Conversely, RasGRP1 expression in tTregs increases when TGF‐β signaling is inhibited. Together, these data show that RasGRP1 expression is repressed in tTregs by TGF‐β signaling and suggests that reduced RasGRP1 expression is critical for tTregs to resist apoptosis caused by continuous antigen exposure.
Accuracy of anogenital distance and anti‐Müllerian hormone in the diagnosis of endometriosis without surgery
Authors: Sánchez‐Ferrer María L. , Jiménez‐Velázquez Raquel , Mendiola Jaime , Prieto‐Sánchez María T. , Cánovas‐López Laura , Carmona‐Barnosi Ana , Corbalán‐Biyang Shiana , Hernández‐Peñalver Ana I. , Adoamnei Evdochia , Nieto Aníbal , Torres‐Cantero Alberto M. 
Published: October 2018

AbstractObjectiveTo assess the predictive ability of a combination of anogenital distance (AGD) and anti‐Müllerian hormone (AMH) to diagnosis the presence of endometriosis without surgery.MethodsThe present study included women diagnosed with endometriosis and a control group who attended the “Virgen de la Arrixaca” University Hospital, Murcia, Spain, between September 1, 2014, and May 31, 2015. Serum concentrations of AMH were measured, and two AGD measurements were obtained: from the anterior clitoral surface to the upper verge of the anus (AGDAC), and from the posterior fourchette to the upper verge of the anus (AGDAF). Data were assessed by receiver operator characteristic (ROC) curves.ResultsWomen in the endometriosis group (n=57) had significantly shorter AGDAF (22.8 ± 4.6 vs 27.2 ± 5.7 mm; P<0.001) and lower AMH (2.2 ± 2.5 vs 3.3 ± 1.9 ng/mL; P<0.003) compared with the control group (n=93). Women with serum AMH below the clinical cut‐off (1 ng/mL) were 17.40‐times more likely to have endometriosis (95% confidence interval [CI] 5.64–53.82). The area under the ROC curve of combined AMH and AGDAF was 0.77 (95% CI 0.70–0.85).ConclusionThe model for predicting endometriosis on the basis of AMH and AGD could be useful for clinicians and epidemiologists to improve diagnosis and prognosis of this condition.
Front Cover: Photoacoustic microscopy for evaluating combretastatin A4 phosphate induced vascular disruption in orthotopic glioma (J. Biophotonics 10/2018)
Authors: Bi Renzhe , Balasundaram Ghayathri , Jeon Seungwan , Tay Hui Chien , Pu Yang , Li Xiuting , Moothanchery Mohesh , Kim Chulhong , Olivo Malini 
Published: October 2018

Optical resolution photoacoustic microscopy (OR‐PAM) imaging system is exploited to evaluate the vascular disruptive effect of Combretastatin A4 Phosphate (CA4P), a solid tumor drug, on a murine orthotopic glioma with intact skull. Hemodynamic changes in tumor vasculature are in agreement with the well documented shutdown and recovery associated CA4P administration. High resolution vasculature images obtained using OR‐PAM enable mapping of each individual blood vessel's response to the treatment.Further details can be found in the article by Renzhe Bi, Ghayathri Balasundaram, Seungwan Jeon, et al. (e201700327)
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First chemical and sensory characterization of Moribel and Tinto Fragoso wines using HPLC‐DAD‐ESI‐MS/MS, GC‐MS, and Napping® techniques: comparison with Tempranillo
Authors: Pérez‐Navarro José , Izquierdo‐Cañas Pedro M , Mena‐Morales Adela , Martínez‐Gascueña Jesús , Chacón‐Vozmediano Juan L , García‐Romero Esteban , Gómez‐Alonso Sergio , Hermosín‐Gutiérrez Isidro 
Published: October 2018

AbstractBACKGROUNDDue to the current dominance of a few grape varieties in the wine market, the aim of this work was to study the detailed phenolic and volatile composition, chromatic characteristics, and sensorial properties of red wines elaborated with new Vitis vinifera grapes (Moribel and Tinto Fragoso) identified using the High Perfomance Liquid Chromatography‐Diode Array Detector‐Electrospray Ionization‐Tandem Mass Spectrometry (HPLC‐DAD‐ESI‐MS/MS), Gas Chromatography‐ Mass Spectrometry (GC‐MS), CIELab color space, and Napping ® techniques.RESULTSTinto Fragoso wine showed higher phenolic content than Moribel, with more anthocyanins, flavonols, and stilbenes. These wines also contained anthocyanin diglucosides not reported for Vitis vinifera wines. The odor activity values of free volatile compounds were calculated to indicate their influence on wine aroma, the fruity aromas of Moribel standing out particularly. The wines studied were positively evaluated by the tasters. Moribel's sensory profile was characterized by red fruit aromas and Tinto Fragoso showed more aromatic intensity and persistence in the mouth.CONCLUSIONThe results obtained from the first characterization of red wines made from novel Vitis vinifera grapes suggest that Moribel and Tinto Fragoso could be appropriate raw materials for the elaboration of quality young red wines. Tinto Fragoso provided wines with sensorial properties different from those of Tempranillo, and could be an alternative to the well known red wines on the market. © 2018 Society of Chemical Industry