bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synthesis of Indomorphan Pseudo‐Natural Product Inhibitors of Glucose Transporters GLUT‐1 and ‐3
Authors: Ceballos Javier , Schwalfenberg Melanie , Karageorgis George , Reckzeh Elena S. , Sievers Sonja , Ostermann Claude , Pahl Axel , Sellstedt Magnus , Nowacki Jessica , Carnero Corrales Marjorie A. , Wilke Julian , Laraia Luca , Tschapalda Kirsten , Metz Malte , Sehr Dominik A. , Brand Silke , Winklhofer Konstanze , Janning Petra , Ziegler Slava , Waldmann Herbert 
Published: August 2019

AbstractBioactive compound design based on natural product (NP) structure may be limited because of partial coverage of NP‐like chemical space and biological target space. These limitations can be overcome by combining NP‐centered strategies with fragment‐based compound design through combination of NP‐derived fragments to afford structurally unprecedented “pseudo‐natural products” (pseudo‐NPs). The design, synthesis, and biological evaluation of a collection of indomorphan pseudo‐NPs that combine biosynthetically unrelated indole‐ and morphan‐alkaloid fragments are described. Indomorphane derivative Glupin was identified as a potent inhibitor of glucose uptake by selectively targeting and upregulating glucose transporters GLUT‐1 and GLUT‐3. Glupin suppresses glycolysis, reduces the levels of glucose‐derived metabolites, and attenuates the growth of various cancer cell lines. Our findings underscore the importance of dual GLUT‐1 and GLUT‐3 inhibition to efficiently suppress tumor cell growth and the cellular rescue mechanism, which counteracts glucose scarcity.
A Nontrigonal Tricoordinate Phosphorus Ligand Exhibiting Reversible “Nonspectator” L/X‐Switching
Authors: Cleveland Gregory T. , Radosevich Alexander T. 
Published: August 2019

AbstractWe report here a “nonspectator” behavior for an unsupportedL‐function σ3‐P ligand (i.e. P{N[o‐NMe‐C6H4]2},1a) in complex with the cyclopentadienyliron dicarbonyl cation (Fp+). Treatment of1a⋅Fp+with [(Me2N)3S][Me3SiF2] results in fluoride addition to theP‐center, giving the isolable crystalline fluorometallophosphorane1aF⋅Fp that allows a crystallographic assessment of the variance in the Fe−P bond as a function of P‐coordination number. The nonspectator reactivity of1a⋅Fp+is rationalized on the basis of electronic structure arguments and by comparison to trigonal analogue (Me2N)3P⋅Fp+(i.e.1b⋅Fp+), which is inert to fluoride addition. These observations establish a nonspectator L/X‐switching in (σ3‐P)–M complexes by reversible access to higher‐coordinate phosphorus ligand fragments.
Enantioselective Rhodium‐Catalyzed Addition of Arylboroxines to N‐Unprotected Ketimines: Efficient Synthesis of Cipargamin
Authors: Zhu Jinbin , Huang Linwei , Dong Wei , Li Naikai , Yu Xingxin , Deng Wei‐Ping , Tang Wenjun 
Published: August 2019

AbstractHighly enantioselective rhodium‐catalyzed addition of arylboroxines to N‐unprotected ketimines is realized for the first time by employing chiral BIBOP‐type ligands with a Rh loading as low as 1 mol %. A range of chiral α‐trifluoromethyl‐α,α‐diaryl α‐tertiary amines or 3‐amino‐3‐aryloxindoles were formed with excellent ee values and yields by employing either WingPhos or PFBO‐BIBOP as the ligand. The method has enabled an efficient enantioselective synthesis of cipargamin.
An Ultrastable Metal Azolate Framework with Binding Pockets for Optimal Carbon Dioxide Capture
Authors: Wang Zhi‐Shuo , Li Mian , Peng Yun‐Lei , Zhang Zhenjie , Chen Wei , Huang Xiao‐Chun 
Published: August 2019

AbstractIn the evolution of metal–organic frameworks (MOFs) for carbon capture, a lasting challenge is to strike a balance between high uptake capacity/selectivity and low energy cost for regeneration. Meanwhile, these man‐made materials have to survive from practical demands such as stability under harsh conditions and feasibility of scale‐up synthesis. Reported here is a new MOF, Zn(imPim) (aka. MAF‐stu‐1), with an imidazole derivative ligand, featuring binding pockets that can accommodate CO2 molecules in a fit‐like‐a‐glove manner. Such a high degree of shape complementarity allows direct observation of the loaded CO2 in the pockets, and warrants its optimal carbon capture performances exceeding the best‐performing MOFs nowadays. Coupled with the record thermal (up to 680 °C) and chemical stability, as well as rapid large‐scale production, both encoded in the material design, Zn(imPim) represents a most competitive candidate to tackle the immediate problems of carbon dioxide capture.
Towards deep‐blue phosphorescence: molecular design and property prediction of iridium complexes with pyridinylphosphinate ancillary ligand
Authors: Song Chongping , Li Jiaqi , Wang Zhixiang , Chen Yanan , Zhao Fei , Li Ping , Zhang Houyu 
Published: August 2019

A series of iridium complexes (1–5), which consist of two 2‐(2,4‐difluorophenyl)pyridine (dfppy)‐based primary ligands and one pyridinylphosphinate ancillary ligand, have been investigated theoretically for screening highly efficient deep‐blue light‐emitting materials. Compared with the reported dfppy‐based emitter 1, the designed iridium complexes 3–5 with the introduction of a stronger electron‐withdrawing (–CN, –CF3, or o‐carborane) group and a bulky electron‐donating (tert‐butyl) group in dfppy ligands can be achieved to display the emission peaks at 443, 442, and 447 nm, respectively. The electronic structures, absorption and emission properties, radiative and nonradiative processes of their excited states, and charge injection and transport properties of the iridium complexes are analyzed in detail. The calculated results show that designed iridium complexes have comparable radiative and nonradiative rate constants with 1, and are expected to have similar quantum efficiency with 1. Meanwhile, these designed complexes keep the advantages of the charge transport properties of 1, indicating that they are potential iridium complexes for efficient deep‐blue phosphorescence. This work provides more in‐depth understanding the structure–property relationship of dfppy‐based iridium complexes, and shed lights on molecular design for deep‐blue phosphorescent metal complexes.
Bifunctional coordination polymers as efficient catalysts for carbon dioxide conversion
Authors: Arunachalam Rajendran , Chinnaraja Eswaran , Valkonen Arto , Rissanen Kari , Subramanian Palani S. 
Published: August 2019

The multidentate ligand H2L upon complexation with Zn (II) and Cd (II) provide a one‐dimensional polymeric networks. These coordination polymers (CPs) CP‐1 and CP‐2 containing Zn (II) and Cd (II) metals respectively are well characterized. The single crystal structural analysis confirms the formation of one‐dimensional coordination polymer with zigzag fashion in CP‐1 and ladder chain CP‐2. Both the CPs are applied as catalysts to synthesize various cyclic carbonates from epoxides and carbon dioxide. The catalysts are giving better conversion under solvent‐free and additive‐free condition using 10 bar CO2 and 100 °C as optimized pressure and temperature. The detailed kinetic experiments suggesting the first order kinetics, the energy of activation (Ea) is calculated for this catalytic conversion.
Effects of Dehulling Sacha Inchi (Plukenetia volubilis L.) Seeds on the Physicochemical and Sensory Properties of Oils Extracted by Means of Cold Pressing
Authors: Gutiérrez Luis‐Felipe , Sanchez‐Reinoso Zain , Quiñones‐Segura Yolanda 
Published: August 2019

AbstractSacha Inchi (Plukenetia volubilis L.) is a plant native to the Peruvian Amazon, with great expansion because of the high industrialization potential of its seeds (SIS). The Sacha Inchi oil (SIO) is commonly obtained by pressing the SIS, and it is of high commercial value because of its excellent nutritional properties. In this study, we investigated the effects of the dehulling of SIS on the physicochemical and sensory properties of the SIO extracted by means of cold pressing. The fatty acid composition, Fourier transform infrared (FTIR) spectra, density, refractive index (RI), acid value (AV), peroxide value (PV), p‐anisidine index (p‐An), oxidative stability index (OSI), color, and sensory profiles of the SIO samples were evaluated. The oils obtained from whole SIS showed similar fatty acid profiles, physicochemical properties, and sensory profiles to those extracted from dehulled SIS. After 60 days of storage, the total oxidation values of both SIO samples significantly increased, but there were no significant differences between oils from whole and dehulled SIS. Thus, the dehulling process could be avoided without affecting significantly the quality of the obtained oils.
The effect of greenwashing on online consumer engagement: A comparative study in France, Germany, Turkey, and the United Kingdom
Authors: Topal İbrahim , Nart Sima , Akar Cüneyt , Erkollar Alptekin 
Published: August 2019

AbstractThe effect of the Volkswagen emission crisis in 2015, the biggest greenwashing event in recent years, on the online consumer engagement of Facebook brand pages was investigated in France, Germany, Turkey, and the United Kingdom. These countries have been selected for the reason that Volkswagen sales and diesel‐engine cars and the use of social media are quite common. For 6 years in these four countries, the likes, comments, and shares made by consumers on the Facebook brand page of Volkswagen have been examined. The monthly dataset covers January 2012 to December 2017. The obtained data were analyzed with autoregressive–moving average models. Despite a globally positive approach to green products, countries' attitudes toward greenwashing have been significantly different. The findings showed that online consumer engagement was negative in the United Kingdom and Turkey and in a positive direction in Germany, whereas there was no change in France in the fourth quarter of 2015.
Production and characterization of β‐glucosidase from Aspergillus niger fermentation: Application for organic fraction of municipal solid waste hydrolysis and methane enhancement
Authors: Mlaik Najoua , Sayadi Sami , Hamza Manel , Khoufi Sonia 
Published: August 2019

AbstractThe anaerobic digestion of the organic fraction of municipal solid waste (OFMSW) is currently an attractive treatment process with energy production in the form of biogas. Hydrolysis is the rate‐limiting step for the anaerobic digestion of solid wastes. Thus, in the present study fungal enzymatic pretreatment of OFMSW was applied to enhance biogas production. Two enzyme cocktails rich on β‐glucosidase were produced from submerged fermentation of Aspergillus niger on basal medium using OFMSW as carbon source and urea (Urea cocktail) and Ulva rigida as nitrogen source (Ulva cocktail). Ulva cocktail displayed an important effect on OFMSW solubilization. Therefore, an increase of reducing sugar concentration about 60% was obtained which was in correlation with chemical oxygen demand (COD) increase. The performance of enzymatic pretreatment on anaerobic digestion of OFMSW was studied by conducting biochemical methane potential tests. Results showed that the enzymatic pretreatment improved methane yield of OFMSW even at high solid concentration. High methane yield about 500 ml/g total volatile solid was obtained, which corresponds up to 68% enhancement over the control.
Orthodontic Management of a Migrated Maxillary Central Incisor With a Secondary Occlusal Trauma
Authors: Thierens Laurent A.M. , Van de Velde Tommie , De Pauw Guy A.M. 
Published: August 2019

IntroductionNormal or excessive occlusal forces exerted on teeth with a reduced periodontal support might result in a secondary occlusal trauma. This type of injury is diagnosed based on histological changes in the periodontium. Multiple clinical and radiographic indicators are, therefore, required as surrogates to assist the presumptive diagnosis of a (secondary) occlusal trauma.Case PresentationIn this case report, the diagnosis, management, and the 1‐year follow‐up of a secondary occlusal trauma of a maxillary central incisor are described. The occlusal relationship was rehabilitated with fixed orthodontic appliances and was further stabilized with both fixed and removable retainers.ConclusionsA combined periodontal‐orthodontic approach for a secondary occlusal trauma allows the rehabilitation of periodontal, occlusal, and esthetic parameters. Twelve months after the end of the active orthodontic treatment, a combination of fixed and removable retainers showed to be effective in retaining the treatment outcome.
Distinct molecular mechanisms control levels of synaptic F‐actin
Authors: Glebov Oleg O. 
Published: September 2019

AbstractPolymerization of filamentous (F)‐actin at the neuronal synapse plays an important role in neuronal function. However, the regulatory mechanisms controlling the levels of synaptic actin remain incompletely understood. Here, I used established pharmacological blockers to acutely disrupt the function of actin polymerization machinery, then quantified their effect on synaptic F‐actin levels. Synaptic F‐actin was modestly decreased by inhibition of Arp2/3‐dependent actin branching. Blockade of formin‐dependent actin elongation resulted in an Arp2/3‐dependent increase in synaptic actin that could be mimicked by limited actin depolymerization. Limited actin depolymerization was also sufficient to reverse a decrease in synaptic F‐actin caused by prolonged blockade of synaptic NMDA‐type glutamate receptors. These results suggest that interplay between different actin polymerization pathways may regulate synaptic actin dynamics.
Mental health in the criminal justice system: A pathways approach to service and research design
Authors: Forrester Andrew , Hopkin Gareth 
Published: September 2019

AbstractBackgroundCare pathwayapproaches were introduced into health care in the 1980s and have become standard international practice. They are now being introduced more specifically for health care in the criminal justice system. Care pathway delivery has the theoretical advantage of encouraging a whole‐systems approach for health and social care within the criminal justice system, but how well is it supported by empirical evidence?AimsThe aim of this study is to review the nature and extent of evidence streams supporting health care delivery within interagency pathway developments since 2000.MethodWe used an exploratory narrative method to review the nature and extent of evidence streams supporting health care delivery within interagency pathway developments since 2000. The available literature was reviewed using a keyword search approach with three databases: PubMed, Medline, and Google Scholar.FindingsResearch in this field has covered police custody, courts, prisons, and the wider community, but there is little that follows the entire career through all these elements of offender placement. Main themes in the research to date, regardless of where the research was conducted, have been counting the disorder or the need, development and evaluation of screening tools, and evaluation of clinical intervention styles. Most evidence to date is simply observational, although the possibility of conducting randomised controlled trials of interventions within parts of the criminal justice system, especially prisons, is now well established.ConclusionsAccess to health care while passing through the criminal justice system is essential because of the disproportionately high rates of mental disorder among offenders, and the concept of structured pathways to ensure this theoretically satisfying, but as yet empirically unsupported. Further, substantial cuts in services, generally following government economies, are largely unresearched. Considerable investment in new possibilities, driven by both pressure groups and government, tend to be informed by good will and theory rather than hard evidence and are often not evaluated even after introduction. This must change.
Effect of pH and defatting on the functional attributes of safflower, sunflower, canola, and hemp protein concentrates
Authors: Galves Cassia , Stone Andrea K. , Szarko James , Liu Shuanghui , Shafer Kent , Hargreaves Jason , Siarkowski Michael , Nickerson Michael T. 
Published: August 2019

AbstractBackground and objectivesThe effect of defatting four oilseed protein concentrates (safflower, sunflower, canola, and hemp) on the surface and functional properties of the proteins was investigated as a function of pH (pH 3, 5, 7). The functionality of commercial protein concentrates (soy, faba bean, lentil, pea, northern great bean, whey) already in the marketplace was also tested for comparative purposes.FindingsDefatting with hexane increased the protein content from 77.3% to 92.9% for safflower, 67.5 to 75.5% for sunflower, 58.0–66.0% for canola, and 71.0–83.2% for hemp. The approximate isoelectric point (pI) of safflower increased with defatting (5.4–5.8), whereas for canola the pI decreased with defatting (4.7–4.3), and sunflower and hemp protein concentrates had similar pI for defatted or full fat. Certain functional properties were improved with defatting, whereas others showed the opposite trend; this was highly dependent on protein type and pH.ConclusionsThe oilseed concentrates were comparable to the concentrates in the marketplace with canola and sunflower proteins having the greatest oil‐holding capacity and defatted safflower having the highest foaming capacity of all the proteins tested.Significance and noveltyBased on their functionality, the oilseed protein concentrates have potential to be used by the food ingredient industry.
Cobalt‐Embedded N‐Doped Carbon Arrays Derived In Situ as Trifunctional Catalyst Toward Hydrogen and Oxygen Evolution, and Oxygen Reduction
Authors: Huang Niu , Yang Liu , Zhang Mingyi , Yan Shufang , Ding Yuyue , Sun Panpan , Sun Xiaohua 
Published: August 2019

AbstractThe carbons containing metals coordinated with nitrogen are emerging as the most promising catalysts toward various heterogeneous catalyses. In this paper, such a carbon catalyst is prepared through a chemical vapor deposition (CVD)‐supported precursor pyrolysis. Compared with the direct pyrolysis of polypyrrole@cobalt salt precursor, the incorporation of dicyanodiamide as the CVD source facilitates the diversification and hierarchization of carbon morphology, the reduction of Co particle size, and the increase of the proportion of interfacial Co−N−C and pyridinic‐N. The catalyst is composed of in‐situ‐grown multiple‐morphology carbons (MMCs) with metallic Co particles embedded, where the MMCs are a combination of nano‐particles, ‐rods, and ‐wires, all comprised by small N‐doped carbon nanoflakes. Owing to the combined modulation on morphology configurations and defect states, the Co/MMCs catalyst demonstrates excellent activities toward hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). A half‐wave potential of 0.84 V and low overpotentials of 86 and 180 mV at 10 mA cm−2 current density for HER and OER are achieved, respectively. Additionally, the catalyst also demonstrates favorable prospects for large‐scale applications in overall water splitting and Zn‐air battery.
Extending Surface‐Enhanced Raman Spectroscopy to Liquids Using Shell‐Isolated Plasmonic Superstructures
Authors: Wondergem Caterina S. , van Swieten Thomas P. , Geitenbeek Robin G. , Erné Ben H. , Weckhuysen Bert M. 
Published: September 2019

AbstractPlasmonic superstructures (PS) based on Au/SiO2 were prepared for Shell‐Isolated Nanoparticle‐Enhanced Raman Spectroscopy (SHINERS) in liquid phase applications. These superstructures are composed of functionalized SiO2 spheres with plasmonic Au nanoparticles (NPs) on their surface. Functionalization was performed with (3‐aminopropyl)trimethoxysilane, (3‐mercaptopropyl)trimethoxysilane and poly(ethylene‐imine) (PEI). Of these three, PEI‐functionalized spheres showed the highest adsorption density of Au NPs in TEM, UV/Vis and dynamic light scattering (DLS) experiments. Upon decreasing the Au NP/SiO2 sphere size ratio, an increase in adsorption density was also observed. To optimize plasmonic activity, 61 nm Au NPs were adsorbed onto 900 nm SiO2‐PEI spheres and these PS were coated with an ultrathin layer (1–2 nm) of SiO2 to obtain Shell‐Isolated Plasmonic Superstructures (SHIPS), preventing direct contact between Au NPs and the liquid medium. Zeta potential measurements, TEM and SHINERS showed that SiO2 coating was successful. The detection limit for SHINERS using SHIPS and a 638 nm laser was around 10−12 m of Rhodamine (10−15 m for uncoated PS), all with acquisition settings suitable for catalysis applications.
Tailoring Heterometallic Cluster Functional Building Blocks: Synthesis, Separation, Structural and DFT Studies of [Re6−xMoxSe8(CN)6]n−
Authors: Muravieva Viktoria K. , Gayfulin Yakov M. , Prestipino Carmelo , Lemoine Pierric , Ryzhikov Maxim R. , Yanshole Vadim V. , Cordier Stéphane , Naumov Nikolay G. 
Published: August 2019

AbstractInfluence of the metal core composition and geometry on the structure, spectroscopic properties and redox potentials was investigated for the first time for heterometallic (Re/Mo)6 octahedral clusters. The discrete anionic clusters [Re6‐xMoxSe8(CN)6]n− (x=2, 3; n=4, 5) were obtained as individual salts. Their isomeric composition and bond‐length distribution were inspected using a combination of single‐crystal X‐ray structure analysis, NMR, EXAFS, and DFT calculations.
Tailored Transition‐Metal Coordination Environments in Imidazole‐Modified DNA G‐Quadruplexes
Authors: Punt Philip M. , Clever Guido H. 
Published: August 2019

AbstractTwo types of imidazole ligands were introduced both at the end of tetramolecular and into the loop region of unimolecular DNA G‐quadruplexes. The modified oligonucleotides were shown to complex a range of different transition‐metal cations including NiII, CuII, ZnII and CoII, as indicated by UV/Vis absorption spectroscopy and ion mobility mass spectrometry. Molecular dynamics simulations were performed to obtain structural insight into the investigated systems. Variation of ligand number and position in the loop region of unimolecular sequences derived from the human telomer region (htel) allows for a controlled design of distinct coordination environments with fine‐tuned metal affinities. It is shown that CuII, which is typically square‐planar coordinated, has a higher affinity for systems offering four ligands, whereas NiII prefers G‐quadruplexes with six ligands. Likewise, the positioning of ligands in a square‐planar versus tetrahedral fashion affects binding affinities of CuII and ZnII cations, respectively. Gaining control over ligand arrangement patterns will spur the rational development of transition‐metal‐modified DNAzymes. Furthermore, this method is suited to combine different types of ligands, for example, those typically found in metalloenzymes, inside a single DNA architecture.
A Tris(3‐pyridyl)stannane as a Building Block for Heterobimetallic Coordination Polymers and Supramolecular Cages
Authors: Yang Eric S. , Plajer Alex J. , García‐Romero Álvaro , Bond Andrew D. , Ronson Tanya K. , Álvarez Celedonio M. , García‐Rodríguez Raúl , Colebatch Annie L. , Wright Dominic S. 
Published: August 2019

AbstractThe systematic assembly of supramolecular arrangements is a persistent challenge in modern coordination chemistry, especially where further aspects of complexity are concerned, as in the case of large molecular mixed‐metal arrangements. One targeted approach to such heterometallic complexes is to engineer metal‐based donor ligands of the correct geometry to build 3D arrangements upon coordination to other metals. This simple idea has, however, only rarely been applied to main group metal‐based ligand systems. Here, we show that the new, bench‐stable tris(3‐pyridyl)stannane ligand PhSn(3‐Py)3 (3‐Py=3‐pyridyl) provides simple access to a range of heterometallic SnIV/transition metal complexes, and that the presence of weakly coordinating counter anions can be used to build discrete molecular arrangements involving anion encapsulation. This work therefore provides a building strategy in this area, which parallels that of supramolecular transition metal chemistry.