bluuebunny/crossref_metadata_2025_split huggingface dataset:
Palladium(II)‐Catalyzed Regio‐ and Stereoselective Hydroarylation of Diphenylphosphorylallenes with Arylboronic Acids in the Presence of Sodium Hydroxide and Oxygen
Authors: Chen Yang , Ma Dong‐Mei , Ba Fei‐Fei , Sun Jing , Liu Tian , Zhu Lei , Zhou Ming‐Dong 
Published: August 2016

AbstractThe palladium(II)‐catalyzed hydroarylation of diphenylphosphorylallenes (via 1,2‐addition of the allenic double bond) with arylboronic acids in the presence of sodium hydroxide and oxygen is developed. The regioselectivities turn out to be well controlled, affording 2‐aryl‐3‐(diphenylphosphinyl)alkenes as the only product. Moreover, the stereoselectivities for reactions of γ‐substituted allenes can also be nicely controlled, resulting in the formation of Z‐alkenes. The reaction shows high substituent loading capability and tolerance of various substituents. A mechanism, including transmetalation of arylboronic acid with palladium halides, insertion of the 1,2‐allenic double bond to the Pd−Ar bond, and protonation to afford the final hydroarylation product is proposed.magnified image
One‐Pot Quinine‐Catalyzed Synthesis of α‐Chiral γ‐Keto Esters: Enantioenriched Precursors of cis‐α,γ‐Substituted‐γ‐Butyrolactones
Authors: Meninno Sara , Volpe Chiara , Lattanzi Alessandra 
Published: August 2016

AbstractA highly enantioselective one‐pot synthesis of important building blocks, α‐chiral γ‐keto esters, has been developed by combining a quinine‐catalyzed Michael addition of malononitrile to trans‐enones followed by magnesium monoperoxyphthalate (MMPP) oxidation. These synthons proved to be useful reagents for a simple access to challenging cis‐α,γ‐disubstituted γ‐butyrolactones in good diastereoselectivity and high enantiocontrol.magnified image
Photonenenergie als dritte Dimension bei der Analyse der kristallographischen Textur
Authors: Grünewald Tilman A. , Rennhofer Harald , Tack Pieter , Garrevoet Jan , Wermeille Didier , Thompson Paul , Bras Wim , Vincze Laszlo , Lichtenegger Helga C. 
Published: August 2016

AbstractDie herkömmliche Bestimmung der Kristallvorzugsorientierung (kristallographische Textur) beruht auf Röntgenbeugung mit Flächendetektoren und 2D‐Daten. Echte, ortsaufgelöste 3D‐Informationen erfordern eine Probendrehung im Strahl. Dabei wird das beleuchtete Volumen ständig verändert und das Streusignal verschmiert, was die Bestimmung komplexer Strukturen verhindert. Diese Einschränkung lässt sich mit energieauflösender Laue‐Beugung umgehen. Es wurde eine Methode entwickelt, um einen großen Teil des reziproken Raums abzudecken und aus der Energie der Röntgenphotonen die dritte Raumdimension zu errechnen. Das Verfahren wurde auf Kohlenstofffasern und Hummerpanzer, als Beispiel für biomineralisiertes Gewebe, angewendet. Das besondere Potenzial dieser Methode liegt darin, dass sie nur eine einzige Messung erfordert, sowie am direkten Erfassen von 3D‐Informationen ohne Vorwissen über die Probe. Das Verfahren ermöglicht daher das Abrastern großer Proben mit komplexer Struktur und eröffnet die konzeptuelle Möglichkeit, Texturänderungen in situ zu verfolgen, z. B. während Kristallisationsvorgängen.
Glyceride‐Mimetic Prodrugs Incorporating Self‐Immolative Spacers Promote Lymphatic Transport, Avoid First‐Pass Metabolism, and Enhance Oral Bioavailability
Authors: Hu Luojuan , Quach Tim , Han Sifei , Lim Shea F. , Yadav Preeti , Senyschyn Danielle , Trevaskis Natalie L. , Simpson Jamie S. , Porter Christopher J. H. 
Published: August 2016

AbstractFirst‐pass hepatic metabolism can significantly limit oral drug bioavailability. Drug transport from the intestine through the lymphatic system, rather than the portal vein, circumvents first‐pass metabolism. However, the majority of drugs do not have the requisite physicochemical properties to facilitate lymphatic access. Herein, we describe a prodrug strategy that promotes selective transport through the intestinal lymph vessels and subsequent release of drug in the systemic circulation, thereby enhancing oral bioavailability. Using testosterone (TST) as a model high first‐pass drug, glyceride‐mimetic prodrugs incorporating self‐immolative (SI) spacers, resulted in remarkable increases (up to 90‐fold) in TST plasma exposure when compared to the current commercial product testosterone undecanoate (TU). This approach opens new opportunities for the effective development of drugs where oral delivery is limited by first‐pass metabolism and provides a new avenue to enhance drug targeting to intestinal lymphoid tissue.
A Biodegradable Polydopamine‐Derived Electrode Material for High‐Capacity and Long‐Life Lithium‐Ion and Sodium‐Ion Batteries
Authors: Sun Tao , Li Zong‐jun , Wang Heng‐guo , Bao Di , Meng Fan‐lu , Zhang Xin‐bo 
Published: August 2016

AbstractPolydopamine (PDA), which is biodegradable and is derived from naturally occurring products, can be employed as an electrode material, wherein controllable partial oxidization plays a key role in balancing the proportion of redox‐active carbonyl groups and the structural stability and conductivity. Unexpectedly, the optimized PDA derivative endows lithium‐ion batteries (LIBs) or sodium‐ion batteries (SIBs) with superior electrochemical performances, including high capacities (1818 mAh g−1 for LIBs and 500 mAh g−1 for SIBs) and good stable cyclabilities (93 % capacity retention after 580 cycles for LIBs; 100 % capacity retention after 1024 cycles for SIBs), which are much better than those of their counterparts with conventional binders.
Template‐Directed Synthesis of Porous and Protective Core–Shell Bionanoparticles
Authors: Li Shaobo , Dharmarwardana Madushani , Welch Raymond P. , Ren Yixin , Thompson Christina M. , Smaldone Ronald A. , Gassensmith Jeremiah J. 
Published: August 2016

AbstractMetal–organic frameworks (MOFs) are promising high surface area coordination polymers with tunable pore structures and functionality; however, a lack of good size and morphological control over the as‐prepared MOFs has persisted as an issue in their application. Herein, we show how a robust protein template, tobacco mosaic virus (TMV), can be used to regulate the size and shape of as‐fabricated MOF materials. We were able to obtain discrete rod‐shaped TMV@MOF core–shell hybrids with good uniformity, and their diameters could be tuned by adjusting the synthetic conditions, which can also significantly impact the stability of the core–shell composite. More interestingly, the virus particle underneath the MOF shell can be chemically modified using a standard bioconjugation reaction, showing mass transportation within the MOF shell.
Chemische Verzwilligung von Salz und Metall in den Subnitridometallaten Ba23Na11(MN4)4 mit M=V, Nb, Ta
Authors: Wörsching Matthias , Tambornino Frank , Datz Stefan , Hoch Constantin 
Published: August 2016

AbstractDie Subnitridometallate Ba23Na11(MN4)4 (M=V, Nb, Ta) kristallisieren in einem neuen Strukturtyp, in dem sowohl ionische ortho‐Nitridometallat‐Anionen als auch Strukturmotive aus einfachen (inter)metallischen Packungen zu finden sind: Na‐zentrierte [Na8]‐Würfel als Ausschnitte aus der bcc‐Struktur von elementarem Natrium und Na‐zentrierte [Ba10Na2]‐Ikosaeder, wie sie z. B. in Laves‐Phasen vorkommen. Einkristall‐ und Pulverröntgenstrukturanalyse unterstreichen in Kombination mit quantenchemischen Berechnungen der elektronischen Struktur und Raman‐Spektroskopie den Charakter der Subnitridometallate als “chemische Zwillinge”. Sie weisen unabhängige Strukturbausteine mit lokal überwiegend entweder ionischer oder metallischer Bindung in einer insgesamt metallischen Verbindung auf.
Importance of a Fluorine Substituent for the Preparation of meta‐ and para‐Pentafluoro‐λ6‐sulfanyl‐Substituted Pyridines
Authors: Kosobokov Mikhail , Cui Benqiang , Balia Andrii , Matsuzaki Kohei , Tokunaga Etsuko , Saito Norimichi , Shibata Norio 
Published: August 2016

AbstractAlthough there are ways to synthesize ortho‐pentafluoro‐λ6‐sulfanyl (SF5) pyridines, meta‐ and para‐SF5‐substituted pyridines are rare. We disclose herein a general route for their synthesis. The fundamental synthetic approach is the same as reported methods for ortho‐SF5‐substituted pyridines and SF5‐substituted arenes, that is, oxidative chlorotetrafluorination of the corresponding disulfides to give pyridylsulfur chlorotetrafluorides (SF4Cl‐pyridines), followed by chloride/fluoride exchange with fluorides. However, the trick in this case is the presence on the pyridine ring of at least one fluorine atom, which is essential for the successful transformation of the disulfides into m‐and p‐SF5‐pyridines. After enabling the synthesis of an SF5‐substituted pyridine, ortho‐F groups can be efficiently substituted by C, N, S, and O nucleophiles through an SNAr pathway. This methodology provides access to a variety of previously unavailable SF5‐substituted pyridine building blocks.
Contrasting Frustrated Lewis Pair Reactivity with Selenium‐ and Boron‐Based Lewis Acids
Authors: Wilkins Lewis C. , Günther Benjamin A. R. , Walther Melanie , Lawson James R. , Wirth Thomas , Melen Rebecca L. 
Published: August 2016

AbstractThe activation of π‐bonds in diynyl esters has been investigated by using soft and hard Lewis acids. In the case of the soft selenium Lewis acid PhSeCl, sequential activation of the alkyne bonds leads initially to an isocoumarin (1 equiv PhSeCl) and then to a tetracyclic conjugated structure with the isocoumarin subunit fused to a benzoselenopyran (3 equiv PhSeCl). Conversely, the reaction with the hard Lewis acidic borane B(C6F5)3 initiates a cascade reaction to yield a complex π‐conjugated system containing phthalide and indene subunits.
Branched Arylalkenes from Cinnamates: Selectivity Inversion in Heck Reactions by Carboxylates as Deciduous Directing Groups
Authors: Tang Jie , Hackenberger Dagmar , Goossen Lukas J. 
Published: August 2016

AbstractA decarboxylative Mizoroki–Heck coupling of aryl halides with cinnamic acids has been developed in which the carboxylate group directs the arylation into its β‐position before being tracelessly removed through protodecarboxylation. In the presence of a copper/palladium catalyst, both electron‐rich and electron‐deficient aryl bromides and chlorides bearing numerous functionalities were successfully coupled with broadly available cinnamates, with selective formation of 1,1‐disubstituted alkenes. This reaction concept, in which the carboxylate acts as a deciduous directing group, ideally complements traditional 1,2‐selective Heck reactions of styrenes.
Propensity score-based analysis of outcomes of laparoscopic versus open liver resection for colorectal metastases
Authors: Cipriani F , Rawashdeh M , Stanton L , Armstrong T , Takhar A , Pearce N W , Primrose J , Abu Hilal M 
Published: August 2016

Abstract

Background
There is a need for high-level evidence regarding the added value of laparoscopic (LLR) compared with open (OLR) liver resection. The aim of this study was to compare the surgical and oncological outcomes of patients with colorectal liver metastases (CRLM) undergoing LLR and OLR using propensity score matching to minimize bias.

Methods
This was a single-centre retrospective study using a prospective database of patients undergoing liver resection for CRLM between August 2004 and April 2015. Co-variates selected for matching included: number and size of lesions, tumour location, extent and number of resections, phase of surgical experience, location and lymph node status of primary tumour, perioperative chemotherapy, unilobar or bilobar disease, synchronous or metachronous disease. Prematching and postmatching analyses were compared. Surgical and oncological outcomes were analysed.

Results
Some 176 patients undergoing LLR and 191 having OLR were enrolled. After matching, 133 patients from each group were compared. At prematching analysis, patients in the LLR group showed a longer overall survival (OS) and higher R0 rate than those in the OLR group (P = 0·047 and P = 0·030 respectively). Postmatching analyses failed to confirm these results, showing similar OS and R0 rate between the LLR and OLR group (median OS: 55·2 versus 65·3 months respectively, hazard ratio 0·70 (95 per cent c.i. 0·42 to 1·05; P = 0·082); R0 rate: 92·5 versus 86·5 per cent, P = 0·186). The 5-year OS rate was 62·5 (95 per cent c.i. 45·5 to 71·5) per cent) for OLR and 64·3 (48·2 to 69·5) per cent for LLR. Longer duration of surgery, lower blood loss and morbidity, and shorter postoperative stay were found for LLR on postmatching analysis.

Conclusion
Propensity score matching showed that LLR for CRLM may provide R0 resection rates and long-term OS comparable to those for OLR, with lower blood loss and morbidity, and shorter postoperative hospital stay.
Propensity score-matched analysis of robotic versus open surgical enucleation for small pancreatic neuroendocrine tumours
Authors: Tian F , Hong X-F , Wu W-M , Han X-L , Wang M-Y , Cong L , Dai M-H , Liao Q , Zhang T-P , Zhao Y-P 
Published: August 2016

Abstract

Background
Enucleation of pancreatic neuroendocrine tumours (pNETs) via robotic surgery has rarely been described. This study sought to assess the safety and efficiency of robotic surgery for the enucleation of small pNETs.

Methods
A comparison was conducted of enucleation of pNETs smaller than 2 cm by robotic or open surgery between January 2000 and May 2015. Propensity score matching was used to balance sex, age, BMI, tumour location and tumour diameter. Pathological results, safety-related outcomes (postoperative pancreatic fistula (POPF) rate, estimated blood loss, and short-term mortality and morbidity) and efficiency-related outcomes (duration of surgery and postoperative length of hospital stay) were compared between the groups.

Results
A cohort of 120 patients with pNET were enrolled in the study (1 : 1 matched for open or robotic surgery, 60 per group). Ninety-three patients (77·5 per cent) had a grade 1 tumour and 114 (95·0 per cent) had an insulinoma. Robotic surgery had a conversion rate of 5 per cent (3 of 60), and was not associated with an increased POPF rate (10 per cent versus 17 per cent after open surgery; P = 0·283) or grade III–V surgical complications according to the Dindo–Clavien classification (3 versus 10 per cent respectively; P = 0·272). Estimated blood loss was reduced with the robotic approach (32·5 versus 80·0 ml in the open group; P = 0·008), as was duration of surgery (117 versus 150 min; P &lt; 0·001). Length of hospital stay after surgery was similar in the two groups (12·0 versus 13·5 days respectively; P = 0·071).

Conclusion
Robotic surgery for enucleation of pNETs smaller than 2 cm did not increase POPF or major complication rates, and reduced the duration of surgery and estimated blood loss, compared with open surgery. Registration number: NCT02125929 (https://www.clinicaltrials.gov/).
Mandarin functional MRI Language paradigms
Authors: Ci He , van Graan Andre , Gonzálvez Gloria , Thompson Pamela , Hill Andrea , Duncan John S. 
Published: August 2016

AbstractObjectiveThe objective of this study was to implement convenient, fast, and accurate Mandarin task paradigms for functional MRI, and to locate the Chinese language functional areas in frontal and temporal lobes.Materials and MethodsNineteen healthy Chinese volunteers participated in this study, which utilized a block design with four language tasks: auditory naming (AN), picture naming (PN), verbal fluency‐character (VFC), and verbal fluency‐letter (VFL). All functional images were preprocessed by SPM 8, followed by first‐ and second‐level analyses and lateralization index calculation.ResultsGroup analyses showed that for AN and PN, maximal responses were located in the right superior temporal gyrus. The picture naming‐scrambled pictures and faces contrast gave maximal responses in the left fusiform gyrus; VFC in the left middle frontal gyrus and the left superior frontal gyrus. For VFL the maximal response was in the left superior temporal gyrus. There was some inconsistency of activations for individual subjects. At a threshold of Z > 2.5, 10 voxels extent, activations were seen in >50% subjects for AN in the right superior temporal gyrus, the right middle frontal gyrus, and the left middle temporal gyrus, for PN in the right superior temporal gyrus and for picture naming‐scrambled pictures and faces in left inferior frontal gyrus. As a group, the lateralization index of all contrasts were left hemisphere dominant in the frontal lobes. In the temporal lobe, the hemispheric dominance differed for different contrasts.ConclusionThese Chinese language stimulus paradigms activated language areas, and the functional regions of brain in different language tasks, and can now be piloted in clinical studies.
Socioeconomic status, white matter, and executive function in children
Authors: Ursache Alexandra , Noble Kimberly G. ,   the Pediatric Imaging, Neurocognition and Genetics Study
Published: August 2016

AbstractBackgroundA growing body of evidence links socioeconomic status (SES) to children's brain structure. Few studies, however, have specifically investigated relations of SES to white matter structure. Further, although several studies have demonstrated that family SES is related to development of brain areas that support executive functions (EF), less is known about the role that white matter structure plays in the relation of SES to EF. One possibility is that white matter differences may partially explain SES disparities in EF (i.e., a mediating relationship). Alternatively, SES may differentially shape brain‐behavior relations such that the relation of white matter structure to EF may differ as a function of SES (i.e., a moderating relationship).MethodIn a diverse sample of 1082 children and adolescents aged 3–21 years, we examined socioeconomic disparities in white matter macrostructure and microstructure. We further investigated relations between family SES, children's white matter volume and integrity in tracts supporting EF, and performance on EF tasks.ResultsSocioeconomic status was associated with fractional anisotropy (FA) and volume in multiple white matter tracts. Additionally, family income moderated the relation between white matter structure and cognitive flexibility. Specifically, across multiple tracts of interest, lower FA or lower volume was associated with reduced cognitive flexibility among children from lower income families. In contrast, children from higher income families showed preserved cognitive flexibility in the face of low white matter FA or volume. SES factors did not mediate or moderate links between white matter and either working memory or inhibitory control.ConclusionsThis work adds to a growing body of literature suggesting that the socioeconomic contexts in which children develop not only shape cognitive functioning and its underlying neurobiology, but may also shape the relations between brain and behavior.
Dual pharmacological inhibition of glutathione and thioredoxin systems synergizes to kill colorectal carcinoma stem cells
Authors: Tanaka Genki , Inoue Ken‐ichi , Shimizu Takayuki , Akimoto Kazumi , Kubota Keiichi 
Published: August 2016

AbstractNRF2 stabilizes redox potential through genes for glutathione and thioredoxin antioxidant systems. Whether blockade of glutathione and thioredoxin is useful in eliminating cancer stem cells remain unknown. We used xenografts derived from colorectal carcinoma patients to investigate the pharmacological inhibition of glutathione and thioredoxin systems. Higher expression of five glutathione S‐transferase isoforms (GSTA1, A2, M4, O2, and P1) was observed in xenograft‐derived spheroids than in fibroblasts. Piperlongumine (2.5–10 μmol/L) and auranofin (0.25–4 μmol/L) were used to inhibit glutathione S‐transferase π and thioredoxin reductase, respectively. Piperlongumine or auranofin alone up‐regulated the expression of NRF2 target genes, but not TP53 targets. While piperlongumine showed modest cancer‐specific cell killing (IC50 difference between cancer spheroids and fibroblasts: P = 0.052), auranofin appeared more toxic to fibroblasts (IC50 difference between cancer spheroids and fibroblasts: P = 0.002). The synergism of dual inhibition was evaluated by determining the Combination Index, based on the number of surviving cells with combination treatments. Molar ratios indicated synergism in cancer spheroids, but not in fibroblasts: (auranofin:piperlongumine) = 2:5, 1:5, 1:10, and 1:20. Cancer‐specific cell killing was achieved at the following drug concentrations (auranofin:piperlongumine): 0.25:2.5 μmol/L, 0.5:2.5 μmol/L, or 0.25:5 μmol/L. The dual inhibition successfully decreased CD44v9 surface presentation and delayed tumor emergence in nude mouse. However, a small subpopulation persistently survived and accumulated phosphorylated histone H2A. Such “persisters” still retained lesser but significant tumorigenicity. Thus, dual inhibition of glutathione S‐transferase π and thioredoxin reductase could be a feasible option for decreasing the tumor mass and CD44v9‐positive fraction by disrupting redox regulation.
Facilitated Electron Hopping in Nanolayer Oxygen‐Insensitive Glucose Biosensor for Application in a Complex Matrix
Authors: Grattieri Matteo , Tucci Matteo , Bestetti Massimiliano , Trasatti Stefano , Cristiani Pierangela 
Published: August 2016

AbstractElectrochemical experimental evidence of facilitated electron transfer in a sub‐micrometer biosensor is presented. Layer‐by‐layer self‐assembled deposition provides the unique advantage to specifically control the thickness of the biosensors, allowing an oxygen‐insensitive device with a film thickness of 70 nanometers to be obtained. The biosensor is based on a poly(allylamine) osmium redox mediator and glucose 1‐oxidase. The immobilized enzyme contributes to the signal generation through the full biosensor thickness, with no loss of “active enzyme” in the outer layer of the biosensor through reaction with oxygen, as reported in the case of thick redox hydrogels. The application of the biosensor in complex matrices was approached with tests in wastewater. Encapsulation of the biosensor with Nafion® membrane ensured the protection of the enzyme molecules from the external environment, allowing the successful application of the sensor in a complex matrix.
Modulation by Amino Acids: Toward Superior Control in the Synthesis of Zirconium Metal–Organic Frameworks
Authors: Gutov Oleksii V. , Molina Sonia , Escudero‐Adán Eduardo C. , Shafir Alexandr 
Published: August 2016

AbstractThe synthesis of zirconium metal–organic frameworks (Zr MOFs) modulated by various amino acids, including l‐proline, glycine, and l‐phenylalanine, is shown to be a straightforward approach toward functional‐group incorporation and particle‐size control. High yields in Zr‐MOF synthesis are achieved by employing 5 equivalents of the modulator at 120 °C. At lower temperatures, the method provides a series of Zr MOFs with increased particle size, including many suitable for single‐crystal X‐ray diffraction studies. Furthermore, amino acid modulators can be incorporated at defect sites in Zr MOFs with an amino acid/ligand ratio of up to 1:1, depending on the ligand structure and reaction conditions. The MOFs obtained through amino acid modulation exhibit an improved CO2‐capture capacity relative to nonfunctionalized materials.
Synthesis, Structure and Catalytic Activity of NHC–AgI Carboxylate Complexes
Authors: Wong Valerie H. L. , Vummaleti Sai V. C. , Cavallo Luigi , White Andrew J. P. , Nolan Steven P. , Hii King Kuok (Mimi) 
Published: August 2016

AbstractA general synthetic route was used to prepare 15 new N‐heterocyclic carbene (NHC)–AgI complexes bearing anionic carboxylate ligands [Ag(NHC)(O2CR)], including a homologous series of complexes of sterically flexible ITent ligands, which permit a systematic spectroscopic and theoretical study of the structural and electronic features of these compounds. The complexes displayed a significant ligand‐accelerated effect in the intramolecular cyclisation of propargylic amides to oxazolidines. The substrate scope is highly complementary to that previously achieved by NHC–Au and pyridyl–AgI complexes.