bluuebunny/crossref_metadata_2025_split huggingface dataset:
Character evolution and missing (morphological) data across Asteridae
Authors: Stull Gregory W. , Schori Melanie , Soltis Douglas E. , Soltis Pamela S. 
Published: April 2018

Premise of the StudyOur current understanding of flowering plant phylogeny provides an excellent framework for exploring various aspects of character evolution through comparative analyses. However, attempts to synthesize this phylogenetic framework with extensive morphological data sets have been surprisingly rare. Here, we explore character evolution in Asteridae (asterids), a major angiosperm clade, using an extensive morphological data set and a well‐resolved phylogeny.MethodsWe scored 15 phenotypic characters (spanning chemistry, vegetative anatomy, and floral, fruit, and seed features) across 248 species for ancestral state reconstruction using a phylogenetic framework based on 73 plastid genes and the same 248 species.Key ResultsIridoid production, unitegmic ovules, and cellular endosperm were all reconstructed as synapomorphic for Asteridae. Sympetaly, long associated with asterids, shows complex patterns of evolution, suggesting it arose several times independently within the clade. Stamens equal in number to the petals is likely a synapomorphy for Gentianidae, a major asterid subclade. Members of Lamianae, a major gentianid subclade, are potentially diagnosed by adnate stamens, unilacunar nodes, and simple perforation plates.ConclusionsThe analyses presented here provide a greatly improved understanding of character evolution across Asteridae, highlighting multiple characters potentially synapomorphic for major clades. However, several important parts of the asterid tree are poorly known for several key phenotypic features (e.g., degree of petal fusion, integument number, nucellus type, endosperm type, iridoid production). Further morphological, anatomical, developmental, and chemical investigations of these poorly known asterids are critical for a more detailed understanding of early asterid evolution.
Supporting Mentoring Relationships of Youth in Foster Care: Do Program Practices Predict Match Length?
Authors: Stelter Rebecca L. , Kupersmidt Janis B. , Stump Kathryn N. 
Published: April 2018

AbstractImplementation of research‐ and safety‐based program practices enhance the longevity of mentoring relationships, in general; however, little is known about how mentoring programs might support the relationships of mentees in foster care. Benchmark program practices and Standards in the Elements of Effective Practice for Mentoring, 3rd Edition (MENTOR, 2009) were assessed in the current study as predictors of match longevity. Secondary data analyses were conducted on a national agency information management database from 216 Big Brothers Big Sisters agencies serving 641 youth in foster care and 70,067 youth not in care from across the United States (Mean = 11.59 years old at the beginning of their matches) in one‐to‐one, community‐based (55.06%) and school‐ or site‐based (44.94%) matches. Mentees in foster care had shorter matches and matches that were more likely to close prematurely than mentees who were not in foster care. Agency leaders from 32 programs completed a web‐based survey describing their policies and practices. The sum total numbers of Benchmark program practices and Standards were associated with match length for 208 mentees in foster care; however, neither predicted premature match closure. Results are discussed in terms of how mentoring programs and their staff can support the mentoring relationships of high‐risk youth in foster care.
Intermolecular Electronic Communication in Tetrathiafulvalene Derivatives with Hydrogen‐Bonding Amide Units
Authors: Kaneko Ryuji , Wu Guohua , Sugawa Kosuke , Otsuki Joe 
Published: April 2018

AbstractAs a basis for the design of electroactive materials, mono‐ and bis‐tetrathiafulvalene (TTF) derivatives with one and two amide units were prepared to investigate how hydrogen bonding induces electronic communication. The bis‐TTF compound exhibited a mixed‐valence state as a result of electronic interactions among the TTF units. Comparison with non‐hydrogen‐bonding N‐methylated analogues indicated that the electronic interaction observed occurs between intermolecular TTF units owing to the formation of supramolecular assemblies induced by hydrogen bonds.
Chiral Atropisomeric Indenocorannulene Bowls: Critique of the Cahn–Ingold–Prelog Conception of Molecular Chirality
Authors: Wang Yujia , Allemann Oliver , Balaban T. Silviu , Vanthuyne Nicolas , Linden Anthony , Baldridge Kim K. , Siegel Jay S. 
Published: April 2018

AbstractChiral corannulenes abound, but suffer generally from configurational lability associated with bowl‐to‐bowl inversion, thus obviating questions of stereogenicity and stereoelement construction. In contrast, peri‐annulated corannulenes show greatly increased barriers for bowl‐to‐bowl inversion; specifically indenocorannulenes invert on a time scale too slow to observe by normal NMR methods and raise the possibility of creating chiral atropisomeric bowl‐shaped aromatics. Two methods for preparing indenocorannulene from simple 2‐haloarylcorannulenes—silyl cation C–F activation, and Pd‐mediated C–Cl activation[5]—enable the synthesis of an array of such chiral atropisomeric indenocorannulenes. Resolution of the enantiomers by high‐performance liquid chromatography over chiral support phases motivates the study of chiroptical properties, the assignment of absolute “Cartesian” configuration, and the assessment of configurational stability. These studies bring into question any systematic assignment of nontrivial stereoelements (i.e. not the molecule in its entirety) and refute any assertion of congruence between “Cahn–Ingold–Prelog elements” and the physical or “Cartesian” basis of chirality.
Spatially Confined Assembly of Monodisperse Ruthenium Nanoclusters in a Hierarchically Ordered Carbon Electrode for Efficient Hydrogen Evolution
Authors: Wang Zhong‐Li , Sun Keju , Henzie Joel , Hao Xianfeng , Li Cuiling , Takei Toshiaki , Kang Yong‐Mook , Yamauchi Yusuke 
Published: April 2018

AbstractThe redox units of polyaniline (PAni) are used cooperatively, and in situ, to assemble ruthenium (Ru) nanoclusters in a hierarchically ordered carbon electrode. The oxidized quinonoid imine (QI) units in PAni bond Ru complex ions selectively, whereas reduced benzenoid amine (BA) units cannot. By electrochemically tuning the ratio of QI to BA, Ru complexes are spatially confined in the outer layer of hierarchical PAni frameworks. Carbonization of Ru‐PAni hybrids induces nucleation on the outer surface of the carbon support, generating nearly monodisperse Ru nanoclusters. The optimized catalyst has a low loading of approximately 2 wt % Ru, but exhibits a mass activity for the hydrogen evolution reaction that is about 6.8 times better than commercial 20 wt % Pt/C catalyst.
Generierung von Aryl‐ und Heteroarylmagnesium‐Reagenzien in Toluol mittels Br/Mg‐ oder Cl/Mg‐Austausch
Authors: Ziegler Dorothée S. , Karaghiosoff Konstantin , Knochel Paul 
Published: April 2018

AbstractDas Alkylmagnesiumalkoxid sBuMgOR⋅LiOR (R=2‐Ethylhexyl), das als eine 1.5 m Lösung in Toluol hergestellt wurde, ermöglicht einen sehr schnellen Br/Mg‐Austausch mit Aryl‐ und Heteroarylbromiden, wobei Aryl‐ und Heteroarylalkoxide (ArMgOR⋅LiOR) in Toluol gebildet werden. Diese Grignard‐Reagenzien reagieren mit einer Vielzahl an Elektrophilen, einschließlich Aldehyden, Ketonen, Iminen, Allylbromiden, Acylchloriden, Epoxiden und Aziridinen in guten Ausbeuten. Bemerkenswerterweise ermöglicht das ähnliche Reagenz sBu2Mg⋅2 LiOR einen Cl/Mg‐Austausch mit verschiedenen elektronenreichen Arylchloriden in Toluol, wobei Diorganomagnesiumspezies des Typs Ar2Mg⋅2 LiOR gebildet werden, die gut mit Aldehyden und Allylbromiden reagieren.
Rational Fabrication of Anti‐Freezing, Non‐Drying Tough Organohydrogels by One‐Pot Solvent Displacement
Authors: Chen Fan , Zhou Dan , Wang Jiahui , Li Tianzhen , Zhou Xiaohu , Gan Tiansheng , Handschuh‐Wang Stephan , Zhou Xuechang 
Published: April 2018

AbstractTough hydrogels, polymeric network structures with excellent mechanical properties (such as high stretchability and toughness), are emerging soft materials. Despite their remarkably mechanical features, tough hydrogels exhibit two flaws (freezing around the icing temperatures of water and drying under arid conditions). Inspired by cryoprotectants (CPAs) used in the inhibition of the icing of water in biological samples, a versatile and straightforward method is reported to fabricate extreme anti‐freezing, non‐drying CPA‐based organohydrogels with long‐term stability by partially displacing water molecules within the pre‐fabricated hydrogels. CPA‐based Ca‐alginate/polyacrylamide (PAAm) tough hydrogels were successfully fabricated with glycerol, glycol, and sorbitol. The CPA‐based organohydrogels remain unfrozen and mechanically flexible even up to −70 °C and are stable under ambient conditions or even vacuum.
Creating a Low‐Potential Redox Polymer for Efficient Electroenzymatic CO2 Reduction
Authors: Yuan Mengwei , Sahin Selmihan , Cai Rong , Abdellaoui Sofiene , Hickey David P. , Minteer Shelley D. , Milton Ross D. 
Published: April 2018

AbstractIncreasing greenhouse gas emissions have resulted in greater motivation to find novel carbon dioxide (CO2) reduction technologies, where the reduction of CO2 to valuable chemical commodities is desirable. Molybdenum‐dependent formate dehydrogenase (Mo‐FDH) from Escherichia coli is a metalloenzyme that is able to interconvert formate and CO2. We describe a low‐potential redox polymer, synthesized by a facile method, that contains cobaltocene (grafted to poly(allylamine), Cc‐PAA) to simultaneously mediate electrons to Mo‐FDH and immobilize Mo‐FDH at the surface of a carbon electrode. The resulting bioelectrode reduces CO2 to formate with a high Faradaic efficiency of 99±5 % at a mild applied potential of −0.66 V vs. SHE.
Stishovite's Relative: A Post‐Coesite Form of Phosphorus Oxonitride
Authors: Vogel Sebastian , Baumann Dominik , Niklaus Robin , Bykova Elena , Bykov Maxim , Dubrovinskaia Natalia , Dubrovinsky Leonid , Schnick Wolfgang 
Published: April 2018

AbstractPhosphorus oxonitride (PON) is isoelectronic with SiO2 and may exhibit a similar broad spectrum of intriguing properties as silica. However, PON has only been sparsely investigated under high‐pressure conditions and there has been no evidence on a PON polymorph with a coordination number of P greater than 4. Herein, we report a post‐coesite (pc) PON polymorph exhibiting a stishovite‐related structure with P in a (5+1) coordination. The pc‐PON was synthesized using the multianvil technique and characterized by powder X‐ray diffraction, solid‐state NMR spectroscopy, TEM measurements and in situ synchrotron X‐ray diffraction in diamond anvil cells. The structure model was verified by single‐crystal X‐ray diffraction at 1.8 GPa and the isothermal bulk modulus of pc‐PON was determined to K0=163(2) GPa. Moreover, an orthorhombic PON polymorph (o‐PON) was observed under high‐pressure conditions and corroborated as the stable modification at pressures above 17 GPa by DFT calculations.
Generation of Aryl and Heteroaryl Magnesium Reagents in Toluene by Br/Mg or Cl/Mg Exchange
Authors: Ziegler Dorothée S. , Karaghiosoff Konstantin , Knochel Paul 
Published: April 2018

AbstractThe alkylmagnesium alkoxide sBuMgOR⋅LiOR (R=2‐ethylhexyl), which was prepared as a 1.5 m solution in toluene, undergoes very fast Br/Mg exchange with aryl and heteroaryl bromides, producing aryl and heteroaryl magnesium alkoxides (ArMgOR⋅LiOR) in toluene. These Grignard reagents react with a broad range of electrophiles, including aldehydes, ketones, allyl bromides, acyl chlorides, epoxides, and aziridines, in good yields. Remarkably, the related reagent sBu2Mg⋅2 LiOR (R=2‐ethylhexyl) undergoes Cl/Mg exchange with various electron‐rich aryl chlorides in toluene, producing diorganomagnesium species of type Ar2Mg⋅2 LiOR, which react well with aldehydes and allyl bromides.
Investigation on hydrates blockage and restart process mechanisms of CO2 hydrate slurry flow
Authors: Shi Bo‐Hui , Ding Lin , Li Wen‐Qing , Lv Xiao‐Fang , Liu Yang , Song Shang‐Fei , Ruan Chao‐Yu , Wu Hai‐Hao , Wang Wei , Gong Jing 
Published: April 2018

AbstractBeing an alternative environment‐friendly fluid for the refrigeration process, CO2 hydrate slurry is undesired to result in hydrate blocking in the system. A series of water‐based CO2 hydrate slurry experiments were conducted to investigate hydrate blockages in a high‐pressure flow loop. Blocking would occur soon after CO2 hydrate formation onset. Rapid restart process after the first blocking was found to have serious consequence by inducing a fast hydrate regrowth and an irreversible secondary blocking. The mechanisms of the first blocking and the secondary blocking after the restart process were proposed, based on the observed phenomena and the particle chord length distribution data recorded by focused beam reflectance measurement probe. The influences of the initial flow rate on the supercooling, the induction time, the restart time, and the required time for the secondary blocking after the restart process were analyzed. The understanding on the blocking and restart process mechanisms of CO2 hydrate slurry is important not only in the development of hydrate‐based refrigeration system but also in the field of flow assurance in the oil and gas pipeline or for other applications such as the replacement of methane by CO2 in the naturally occurring hydrate exploration.
Biological evaluation of selected 3,4‐dihydro‐2(1H)‐quinoxalinones and 3,4‐dihydro‐1,4‐benzoxazin‐2‐ones: Molecular docking study
Authors: Petronijević Jelena , Janković Nenad , Stanojković Tatjana P. , Joksimović Nenad , Grozdanić Nađa Đ. , Vraneš Milan , Tot Aleksandar , Bugarčić Zorica 
Published: April 2018

AbstractIn order to investigate new potential therapeutically active agents, we investigated the biological properties of two small libraries of quinoxalinones and 1,4‐benzoxazin‐2‐ones. The results obtained showed that compounds 5, 9–11 have good cytotoxic activity against HeLa cells where the lowest IC50 value (10.46 ± 0.82 μM/mL) was measured for compound 10. Additionally, the most active compounds (5, 9–11) showed much better selectivity for MRC‐5 cells (up to 17.4) compared to cisplatin. In vitro evaluation of the inhibition of the enzyme α‐glucosidase showed that compounds 10 and 11 exert significant inhibition of the enzyme at 52.54 ± 0.09 and 40.09 ± 0.49 μM, respectively. Competitive experiments with ethidium bromide (EB) indicated that all tested compounds have affinity to displace EB from the EB‐DNA complex through intercalation, suggesting good competition with EB (Ksv = (3.1 ± 0.2), (5.1 ± 0.1), (5.6 ± 0.2), and (6.3 ± 0.2) × 103 M−1). A molecular docking study was also performed to better understand the binding modes and to conclude the structure–activity relationships of the synthesized compounds.
Design and synthesis of novel annulated thienopyrimidines as phosphodiesterase 5 (PDE5) inhibitors
Authors: El‐Sharkawy Lina Y. , El‐Sakhawy Rowaida A. , Abdel‐Halim Mohammad , Lee Kevin , Piazza Gary A. , Ducho Christian , Hartmann Rolf W. , Abadi Ashraf H. 
Published: April 2018

AbstractNovel cycloalkene‐fused thienopyrimidine analogues with enhanced phosphodiesterase 5 (PDE5) inhibitory properties are presented. The structure of the reported scaffold was modulated through variation of the terminal cycloalkene ring size, as well as by varying the substituents at position 4 through the attachment of different groups including aniline, benzylamine, cyclohexylethylamine, methyl/acetyl/aryl piperazines, and aryl hydrazones. Compound 15Y with a benzylamine substituent and cycloheptene as terminal ring showed the highest PDE5 inhibitory activity with an IC50 value as low as 190 nM and with good selectivity versus PDE7 and PDE9.
Facile N‐Alkylation/N′‐Arylation Process: A Direct Approach to Aromatic Aminoalkyl Amines
Authors: Zhu Qiming , Chen Mingwei , Hu Jinyu , Yang Luyi 
Published: April 2018

AbstractAn intriguing C−N transformation involving a catalyst‐free N‐alkylation/N′‐arylation process in a multicomponent reaction with secondary amines, cyclic tertiary amines and electron‐deficient aryl halides has been described. In this case, the N‐alkylation of secondary amines, utilizing cyclic tertiary amines as alkyl group sources, is enabled by a facile C−N cleavage. Such an operationally simple method could facilitate access to aromatic aminoalkyl amines, nitrogen‐containing bioactive molecules, in good to excellent yields.
Hyperactive cyclic motor activity in the distal colon after colonic surgery as defined by high-resolution colonic manometry
Authors: Vather R , O'Grady G , Lin A Y , Du P , Wells C I , Rowbotham D , Arkwright J , Cheng L K , Dinning P G , Bissett I P 
Published: April 2018

AbstractBackgroundRecovery after colonic surgery is invariably delayed by disturbed gut motility. It is commonly assumed that colonic motility becomes quiescent after surgery, but this hypothesis has not been evaluated rigorously. This study quantified colonic motility through the early postoperative period using high-resolution colonic manometry.MethodsFibre-optic colonic manometry was performed continuously before, during and after surgery in the left colon and rectum of patients undergoing right hemicolectomy, and in healthy controls. Motor events were characterized by pattern, frequency, direction, velocity, amplitude and distance propagated.ResultsEight patients undergoing hemicolectomy and nine healthy controls were included in the study. Colonic motility became markedly hyperactive in all operated patients, consistently dominated by cyclic motor patterns. Onset of cyclic motor patterns began to a minor extent before operation, occurring with increasing intensity nearer the time of surgery; the mean(s.d.) active duration was 12(7) per cent over 3 h before operation and 43(17) per cent within 1 h before surgery (P = 0.024); in fasted controls it was 2(4) per cent (P &lt; 0·001). After surgery, cyclic motor patterns increased markedly in extent and intensity, becoming nearly continuous (active duration 94(13) per cent; P &lt; 0·001), with peak frequency 2–4 cycles per min in the sigmoid colon. This postoperative cyclic pattern was substantially more prominent than in non-operative controls, including in the fed state (active duration 27(20) per cent; P &lt; 0·001), and also showed higher antegrade velocity (P &lt; 0·001).ConclusionDistal gut motility becomes markedly hyperactive with colonic surgery, dominated by cyclic motor patterns. This hyperactivity likely represents a novel pathophysiological aspect of the surgical stress response. Hyperactive motility may contribute to gut dysfunction after surgery, potentially offering a new therapeutic target to enhance recovery.
Trends in use of lymphadenectomy in surgery with curative intent for intrahepatic cholangiocarcinoma
Authors: Zhang X -F , Chakedis J , Bagante F , Chen Q , Beal E W , Lv Y , Weiss M , Popescu I , Marques H P , Aldrighetti L , Maithel S K , Pulitano C , Bauer T W , Shen F , Poultsides G A , Soubrane O , Martel G , Groot Koerkamp B , Guglielmi A , Itaru E , Pawlik T M 
Published: April 2018

Abstract

Background
The role of routine lymph node dissection (LND) in the surgical treatment of intrahepatic cholangiocarcinoma (ICC) remains controversial. The objective of this study was to investigate the trends of LND use in the surgical treatment of ICC.

Methods
Patients undergoing curative intent resection for ICC in 2000–2015 were identified from an international multi-institutional database. Use of lymphadenectomy was evaluated over time and by geographical region (West versus East); LND use and final nodal status were analysed relative to AJCC T categories.

Results
Among the 1084 patients identified, half (535, 49·4 per cent) underwent concomitant hepatic resection and LND. Between 2000 and 2015, the proportion of patients undergoing LND for ICC nearly doubled: 44·4 per cent in 2000 versus 81·5 per cent in 2015 (P &lt; 0·001). Use of LND increased over time among both Eastern and Western centres. The odds of LND was associated with the time period of surgery and the extent of the tumour/T status (referent T1a: OR 2·43 for T2, P = 0·001; OR 2·13 for T3, P = 0·016). Among the 535 patients who had LND, lymph node metastasis (LNM) was noted in 209 (39·1 per cent). Specifically, the incidence of LNM was 24 per cent in T1a disease, 22 per cent in T1b, 42·9 per cent in T2, 48 per cent in T3 and 66 per cent in T4 (P &lt; 0·001). AJCC T3 and T4 categories, harvesting of six or more lymph nodes, and presence of satellite lesions were independently associated with LNM.

Conclusion
The rate of LNM was high across all T categories, with one in five patients with T1 disease having nodal metastasis. The trend in increased use of LND suggests a growing adoption of AJCC recommendations in the treatment of ICC.
Fast and sensitive HPLC/UV method for cefazolin quantification in plasma and subcutaneous tissue microdialysate of humans and rodents applied to pharmacokinetic studies in obese individuals
Authors: Palma Eduardo Celia , Laureano João Victor , de Araújo Bibiana Verlindo , Meinhardt Nelson Guardiola , Stein Airton Tetelbom , Dalla Costa Teresa 
Published: April 2018

AbstractAntimicrobial prophylactic dosing of morbidly obese patients may differ from normal weighted individuals owing to alterations in drug tissue distribution. Drug subcutaneous tissue distribution can be investigated by microdialysis patients and animals. The need for cefazolin prophylactic dose adjustment in obese patients remains under discussion. The paper describes the validation of an HPLC‐UV method for cefazolin quantification in plasma and microdialysate samples from clinical and pre‐clinical studies. A C18 column with an isocratic mobile phase was used for drug separation, with detection at 272 nm. Total and unbound cefazolin lower limit of quantitation was 5 μg/mL in human plasma, 2 μg/mL in rat plasma, and 0.5 and 0.025 μg/mL in human and rat microdialysate samples, respectively. The maximum intra‐ and inter‐day imprecisions were 10.7 and 8.1%, respectively. The inaccuracy was <9.7%. The limit of quantitation imprecision and inaccuracy were < 15%. Cefazolin stability in the experimental conditions was confirmed. Cefazolin plasma concentrations and subcutaneous tissue penetration were determined by microdialysis in morbidly obese patients (2 g i.v. bolus) and diet‐induced obese rats (30 mg/kg i.v. bolus) using the method. This method has the main advantages of easy plasma clean‐up and practicability and has proven to be useful in cefazolin clinical and pre‐clinical pharmacokinetic investigations.