bluuebunny/crossref_metadata_2025 huggingface dataset:
Mechanofluorochromic Carbon Nanodots: Controllable Pressure‐Triggered Blue‐ and Red‐Shifted Photoluminescence
Authors: Liu Cui , Xiao Guanjun , Yang Mengli , Zou Bo , Zhang Zhi‐Ling , Pang Dai‐Wen
Published: December 2017

Mechanofluorochromic materials, which change their photoluminescence (PL) colors in responding to mechanical stimuli, can be used as mechanosensors, security papers, and photoelectronic devices. However, traditional mechanofluorochromic materials can only be adjusted to a monotone direction upon the external stimuli. Controllable pressure‐triggered blue‐ and red‐shifted PL is reported for C‐dots. The origin of mechanofluorochromism (MFC) in C‐dots is interpreted based on structure–property relationships. The carbonyl group and the π‐conjugated system play key roles in the PL change of C‐dots under high pressure. As the pressure increases, the enhanced π–π stacking of the π‐conjugated system causes the red‐shift of PL, while the conversion of carbonyl groups eventually induces a blue‐shift. Together with their low toxicity, good hydrophilicity, and small size, the tunable MFC property would boost various potential applications of C‐dots.
A Non‐Competitive Inhibitor of VCP/p97 and VPS4 Reveals Conserved Allosteric Circuits in Type I and II AAA ATPases
Authors: Pöhler Robert , Krahn Jan H. , van den Boom Johannes , Dobrynin Grzegorz , Kaschani Farnusch , Eggenweiler Hans‐Michael , Zenke Frank T. , Kaiser Markus , Meyer Hemmo
Published: December 2017

AAA ATPases have pivotal functions in diverse cellular processes essential for survival and proliferation. Revealing strategies for chemical inhibition of this class of enzymes is therefore of great interest for the development of novel chemotherapies or chemical tools. Here, we characterize the compound MSC1094308 as a reversible, allosteric inhibitor of the type II AAA ATPase human ubiquitin‐directed unfoldase (VCP)/p97 and the type I AAA ATPase VPS4B. Subsequent proteomic, genetic and biochemical studies indicate that MSC1094308 binds to a previously characterized drugable hotspot of p97, thereby inhibiting the D2 ATPase activity. Our results furthermore indicate that a similar allosteric site exists in VPS4B, suggesting conserved allosteric circuits and drugable sites in both type I and II AAA ATPases. Our results may thus guide future chemical tool and drug discovery efforts for the biomedically relevant AAA ATPases.
Hydrolysis Batteries: Generating Electrical Energy during Hydrogen Absorption
Authors: Xiao Rui , Chen Jun , Fu Kai , Zheng Xinyao , Wang Teng , Zheng Jie , Li Xingguo
Published: December 2017

The hydrolysis reaction of aluminum can be decoupled into a battery by pairing an Al foil with a Pd‐capped yttrium dihydride (YH2–Pd) electrode. This hydrolysis battery generates a voltage around 0.45 V and leads to hydrogen absorption into the YH2 layer. This represents a new hydrogen absorption mechanism featuring electrical energy generation during hydrogen absorption. The hydrolysis battery converts 8–15 % of the thermal energy of the hydrolysis reaction into usable electrical energy, leading to much higher energy efficiency compared to that of direct hydrolysis.
Efficient Synthesis of Arylated Furans by a Sequential Rh‐Catalyzed Arylation and Cycloisomerization of Cyclopropenes
Authors: Wang Xiaoming , Lerchen Andreas , Daniliuc Constantin G. , Glorius Frank
Published: December 2017

A novel and efficient strategy for the synthesis of arylated furans was successfully developed by a RhIII‐catalyzed coupling of N‐phenoxyacetamides and cyclopropenyl esters. Mechanistic investigation reveals that the arylated furans are formed via arylation of the cyclopropenyl esters followed by cycloisomerization.
Site‐ and Enantioselective C−H Oxygenation Catalyzed by a Chiral Manganese Porphyrin Complex with a Remote Binding Site
Authors: Burg Finn , Gicquel Maxime , Breitenlechner Stefan , Pöthig Alexander , Bach Thorsten
Published: December 2017

A chiral manganese porphyrin complex with a two‐point hydrogen‐bonding site was prepared and probed in catalytic C−H oxygenation reactions of 3,4‐dihydroquinolones. The desired oxygenation occurred with perfect site selectivity at the C4 methylene group and with high enantioselectivity in favor of the respective 4S‐configured secondary alcohols (12 examples, 29–97 % conversion, 19–68 % yield, 87–99 % ee). Mechanistic studies support the hypothesis that the reaction proceeds through a rate‐ and selectivity‐determining attack of the reactive manganese oxo complex at the hydrogen‐bound substrate and an oxygen transfer by a rebound mechanism.
Synthesis, characterization, DNA binding, apoptosis and molecular docking of three Mn(II), Zn(II) and Cu(II) complexes with terpyridine‐based carboxylic acid
Authors: Gao En‐Jun , Feng Yun‐Hui , Su Jun‐Qi , Meng Bo , Jia Bing , Qi Zhen‐Zhen , Peng Ting‐Ting , Zhu Ming‐Chang
Published: December 2017

A series of novel cytotoxic compounds, [Mn(cpt)2], [Zn(tpt)(H2O)2]⋅DMA⋅2(H2O) and [Cu(tpt)]⋅DMA (cpt = 4′‐(4‐carboxyphenyl)‐2,2′:6′,2″‐terpyridine, tpt = 4‐(2,4,6‐tricarboxylphenyl)‐2,2′:6′,2″‐terpyridine, DMA = (CH3)2NH), were isolated and characterized. The structures of these complexes were characterized using single‐crystal X‐ray diffraction. The mode and extent of binding between fish sperm DNA and the complexes were investigated using fluorescence spectroscopy and molecular docking. These results indicate the ability of the complexes to bind to DNA with different binding affinities. The binding of the Zn(II) complex with DNA is stronger than that of the corresponding Cu(II) analogue, which is expected due to the z* effect and geometry. The ability of these complexes to cleave pBR322 plasmid DNA was demonstrated using gel electrophoresis assay, showing that the complexes have effective DNA cleavage activity. In addition, the cytotoxic effects of these complexes were examined on HeLa cells (human cervix epithelia carcinoma cells) in vitro. The three complexes exhibit different cytotoxic effects and decent cancer cell inhibitory rate. This means that the structures and type of metal have a great influence on the activity of these novel complexes.
Unexpected reactivity of pyridinium salts toward alkynyl Fischer complexes to produce oxo‐heterocycles
Authors: Flores‐Conde María Inés , de la Cruz Fabiola N. , López Julio , Jiménez‐Halla J. Óscar C. , Peña‐Cabrera Eduardo , Flores‐Álamo Marcos , Delgado Francisco , Vázquez Miguel A.
Published: December 2017

The unprecedented reaction of ketone‐containing aromatic pyridinium salts 3a‐e and alkynyl Fischer complexes 1a‐f proceeds via a mild domino process to provide 4,6‐disubstituted pyran‐2‐ones 5a‐k and 2,3,5‐trisubstituted furans 6a‐h (45‐97%). According of the results of isotopic labeling experiments, a mechanism involving an initial Michael addition appears to be the key step, obtaining a mesomeric structure responsible for the formation of both products.
Re‐treated nanocellulose whiskers alongside a polyolefin elastomer to toughen and improve polypropylene composites
Authors: Zhang Yajuan , Jiang Xianyou , Bai Zhiwei , Wang Jikui , Qian Ziming , Liu Yaxin
Published: December 2017

Nanocellulose whiskers grafted with a polyolefin elastomer (POE–NCW) were prepared through the reaction of nanocellulose whiskers and a polyolefin elastomer (POE). This was followed by the blending of POE–NCW with polypropylene (PP), and thus, ternary nanocomposites were obtained. When the dosage of POE–NCW was 2%, the tensile strength, storage modulus, and Vicat softening temperature of the ternary nanocomposites increased by 60%, 35%, and 13 °C, respectively. A core–shell‐like cladding structure was formed by the coating of POE on the nanorigid particles; the toughness and rigidity of the composites were both significantly improved, and this prevented brittle fracture under impact and enlarges the range of applications for PP composites. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46066.
Synthesis of a water‐soluble, rubber seed oil–based sulfonate and its tribological properties as a water‐based lubricant additive
Authors: Ding Haiyang , Wang Mei , Li Mei , Huang Kun , Li Shouhai , Xu Lina , Yang Xiaohua , Xia Jianling
Published: December 2017

A novel, water‐based oleic acid (OA)/2‐acryloylamino‐2‐methyl‐1‐propanesulfonic acid (AMPS) copolymer was successfully synthesized as a water‐based lubricant additive. The OA‐AMPS copolymer was characterized by Fourier transform infrared and proton NMR spectroscopies and then used as a lubricant additive in water. The lubrication properties of water‐miscible cutting fluids with the OA‐AMPS copolymer additive were investigated using a four‐ball friction tester. The surface of the wear scars was explored using scanning electron microscopy and X‐ray photoelectron spectroscopy. The addition of the synthesized OA‐AMPS copolymer improved the friction coefficient and wear scar diameter of water. The maximum nonseizure load increased from 95 to 431 N, and the anticorrosion ability on copper was categorized as 1b. Good antiwear and friction‐reducing properties for water were observed and attributed to the absorption and tribochemical films composed of iron oxide and ferrous disulfide. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46119.
Improving the antifouling properties of polypropylene surfaces by melt blending with polyethylene glycol diblock copolymers
Authors: Garle Amit L. , White Fernanda , Budhlall Bridgette M.
Published: December 2017

Protein‐resistant polyethylene‐block‐poly(ethylene glycol) (PE‐b‐PEG) copolymers of different molecular weights at various concentrations were compounded by melt blending with polypropylene (PP) polymers in order to enhance their antifouling properties. Phase separation of the PE‐b‐PEG copolymer and its migration to the surface of the PP blend, was confirmed by attenuated total reflectance–Fourier transform infrared, X‐ray photoelectron spectroscopy, and static water contact angle measurements. Enrichment of PEG chains at the surface of the blends increased with increasing PE‐b‐PEG copolymer concentration and molecular weight. The PP blends compounded with PE‐b‐PEG copolymer having the lowest molecular weight (875 g mol−1), at the lowest concentration (1 wt %), gave the lowest bovine serum protein adsorption (30% less) compared to that of neat PP. At higher concentrations (5 and 10 wt %), and higher molecular weights (920, 1400, and 2250 g mol−1), the PE‐b‐PEG copolymers leached‐out resulting in protein adsorption comparable to that of neat PP. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46122.
Magnetic polystyrene–palygorskite nanocomposite obtained by heterogeneous phase polymerization to apply in the treatment of oily waters
Authors: Middea Antonieta , Spinelli Luciana , Souza Junior Fernando Gomes de , Neumann Reiner , Fernandes Thais , Faulstich Fabiano Richard Leite , Gomes Otavio
Published: December 2017

Water contaminated by oil poses challenges to the management of water resources. Magnetic nanoparticles has been issue of different potential applications including remotion oil from water. Magnetic polystyrene–palygorskite nanocomposites were prepared by a heterogeneous phase polymerization for the removal of organic contaminants from water. The organo‐Fe3O4‐palygorskite nanoparticles were coated with polystyrene, forming water repellent and oil absorbing surfaces to promote the removal of oil from the surfaces of nanocomposites by applying an external magnetic field. X‐ray fluorescence, X‐ray diffraction, scanning electron microscopy, zeta potential and size distribution measurement, surface area determination by BET, density measurement by He pycnometry, carbon grade determination, thermogravimetric analysis, Fourier‐transform infrared spectroscopy, Raman spectroscopy, and evaluation of hydrophobicity by contact angle were used to characterize the nanoparticles. The magnetic nanocomposite obtained showed excellent hydrophobicity, around 78° contact angle. In addition, oil removal capability tests were also performed, according to which the preliminary results indicated removal of approximately 98% of oil in synthetic oily water samples. The oil–water separation using this magnetic nanocomposite provides a promising alternative strategy for water treatment. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46162.
Mushroom polysaccharides‐incorporated cellulose nanofiber films with improved mechanical, moisture barrier, and antioxidant properties
Authors: Fang Donglu , Deng Zilong , Jung Jooyeoun , Hu Qiuhui , Zhao Yanyun
Published: December 2017

Mushroom polysaccharides (MP), including white MP, brown MP, and enoki MP, were incorporated into cellulose nanofiber (CNF). Studies on thermal property, structure, crystallinity, and morphology of CNF‐MP films revealed that MP was well interacted with and adsorbed onto CNF. Incorporation of MP significantly (P < 0.05) increased tensile strength and reduced water vapor permeability of CNF film. CNF‐MP films possessed higher antioxidant activity than CNF only or CNF‐chitosan film, and the antioxidant activity of released components from CNF‐MP films immersed in water was higher than that released from films immersed in methanol. Radical scavenging activity and reducing ability were major antioxidant mechanisms of CNF‐MP films. These trends were consistent with the results of total phenolics content released from films and the antioxidant activity of MP themselves. This study demonstrated CNF‐MP films may be used as packaging material for preventing oxidation and/or dehydration of food during storage. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46166.
Investigation of autophagy and differentiation of myenteric interstitial cells of Cajal in the pathogenesis of gastric motility disorders in rats with functional dyspepsia
Authors: Zhang Li‐min , Zeng Li‐jun , Deng Jing , Zhang Yu‐qin , Wang Yu‐jiao , Xie Tian‐yi , Ling Jiang‐hong
Published: December 2017

Interstitial cells of Cajal (ICC), especially myenteric interstitial cells of Cajal (ICC‐MY), are key to gastrointestinal motility. However, their role in the pathogenesis of functional dyspepsia (FD) is unclear. Therefore, autophagy and differentiation of ICC‐MY were investigated to elucidate the pathogenesis of gastric motility disorder in FD. FD model was induced by chronic stress via tail clamping in rats, which was assessed by the vital signs of rats, gastric emptying rate result, and histology. The ultrastructure of ICC‐MY was examined using transmission electron microscope. In ICC‐MY, changes in autophagic biomarkers (Beclin1 and LC3B) and differentiation biomarkers (c‐kit and SCF) were evaluated with in situ hybridization, quantitative real time PCR, immunofluorescence, and Western blot, respectively. The FD model was successfully induced in rats, as evidenced by the abnormal vital signs (such as loss of appetite, liquid excreta, less activity, and slower weight gain), the decrease in gastric emptying rates, and little pathological change in gastric antrum tissue. Compared with the control group, FD caused increased organelle denaturation or reduction and increase in vacuolization. FD also promoted generation of autophagosomes in ICC‐MY. Moreover, increased the expression of Beclin1 and LC3B, but decreased expression of c‐kit and SCF. Excessive autophagy and abnormal differentiation of ICC‐MY may contribute to the pathogenesis of gastric motility disorder in FD.
Cost comparison by treatment arm and center‐level variations in cost and inpatient days on the phase III high‐risk B acute lymphoblastic leukemia trial AALL0232
Authors: DiNofia Amanda M. , Seif Alix E. , Devidas Meenakshi , Li Yimei , Hall Matthew , Huang Yuan‐Shung V. , Cahen Viviane , Hunger Stephen P. , Winick Naomi J. , Carroll William L. , Fisher Brian T. , Larsen Eric C. , Aplenc Richard
Published: December 2017

The Children's Oncology Group (COG) develops and implements multi‐institutional clinical trials with the primary goal of assessing the efficacy and safety profile of treatment regimens for various pediatric cancers. However, the monetary costs of treatment regimens are not measured. AALL0232 was a COG randomized phase III trial for children with acute lymphoblastic leukemia that found that dexamethasone (DEX) was a more effective glucocorticoid than prednisone (PRED) in patients younger than 10 years, but PRED was equally effective and less toxic in older patients. In addition, high‐dose methotrexate (HD‐MTX) led to better survival than escalating doses of methotrexate (C‐MTX). Cost data from the Pediatric Health Information System database were merged with clinical data from the COG AALL0232 trial. Total and component costs were compared between treatment arms and across hospitals. Inpatient costs were higher in the HD‐MTX and DEX arms when compared to the C‐MTX and PRED arms at the end of therapy. There was no difference in cost between these arms at last follow‐up. Considerable variation in total costs existed across centers to deliver the same therapy that was driven by differences in inpatient days and pharmacy costs. The more effective regimens were found to be more expensive during therapy but were ultimately cost‐neutral in longer term follow‐up. The variations in cost across centers suggest an opportunity to standardize resource utilization for patients receiving similar therapies, which could translate into reduced healthcare expenditures.
Evaluation of β‐Amino Acid Replacements in Protein Loops: Effects on Conformational Stability and Structure
Authors: Mortenson David E. , Kreitler Dale F. , Thomas Nicole C. , Guzei Ilia A. , Gellman Samuel H. , Forest Katrina T.
Published: December 2017

β‐Amino acids have a backbone that is expanded by one carbon atom relative to α‐amino acids, and β residues have been investigated as subunits in protein‐like molecules that adopt discrete and predictable conformations. Two classes of β residue have been widely explored in the context of generating α‐helix‐like conformations: β3‐amino acids, which are homologous to α‐amino acids and bear a side chain on the backbone carbon adjacent to nitrogen, and residues constrained by a five‐membered ring, such the one derived from trans‐2‐aminocyclopentanecarboxylic acid (ACPC). Substitution of α residues with their β3 homologues within an α‐helix‐forming sequence generally causes a decrease in conformational stability. Use of a ring‐constrained β residue, however, can offset the destabilizing effect of α→β substitution. Here we extend the study of α→β substitutions, involving both β3 and ACPC residues, to short loops within a small tertiary motif. We start from previously reported variants of the Pin1 WW domain that contain a two‐, three‐, or four‐residue β‐hairpin loop, and we evaluate α→β replacements at each loop position for each variant. By referral to the ϕ,ψ angles of the native structure, one can choose a stereochemically appropriate ACPC residue. Use of such logically chosen ACPC residues enhances conformational stability in several cases. Crystal structures of three β‐containing Pin1 WW domain variants show that a native‐like tertiary structure is maintained in each case.
Chk1 activation attenuates sensitivity of lapatinib in HER2‐positive gastric cancer
Authors: Bai Ming , Song Na , Che Xiaofang , Wang Xiaoxun , Qu Xiujuan , Liu Yunpeng
Published: December 2017

The ATM and Rad3‐related (ATR)/checkpoint kinase 1 (Chk1) pathway plays a pivotal role in DNA damage sensor and modulating homologous recombination. Recently, emerging evidence demonstrated that Chk1 phosphorylation was associated with chemotherapy and radiotherapy resistance. In this study, we explored the effect of ATR/Chk1 pathway on regulating lapatinib sensitivity in human epidermal growth factor receptor‐2 (HER2)‐positive gastric cancer cell lines. We selected two HER2‐positive gastric cancer cell lines, and NCI‐N87 cells exhibited higher sensitivity than MKN7 cells. Application of lapatinib inhibited phosphorylated HER2 and EGFR and the formation of epidermal growth factor receptor (EGFR)/HER2 complex in both cells. In NCI‐N87 cells, lapatinib induced G1 arrest and reduced Chk1 phosphorylation through inhibiting the expression of DNA topoisomerase 2‐binding protein 1 (TopBP1). While in MKN7 cells, no significant cell cycle transition was found and phosphorylated Chk1 was mildly upregulated. Inhibition of Chk1 phosphorylation enhanced the lapatinib sensitivity of MKN7 cells, which was shown by potentiated anti‐proliferative effect, G1 arrest, downregulation of phosphorylated AKT and ERK along with aggravated DNA damage. In addition, increased Chk1 phosphorylation in NCI‐N87 cells attenuated lapatinib‐induced anti‐proliferative effect and G1 arrest, and abrogated reduced phosphorylated AKT and ERK. Taken together, our study provides a novel mechanism for regulating lapatinib sensitivity in HER2 positive gastric cancer cells, suggesting a new strategy in clinical treatment.
Effect of ECM2 expression on bovine skeletal muscle‐derived satellite cell differentiation
Authors: Liu Chang , Tong Huili , Li Shufeng , Yan Yunqin
Published: December 2017

Extracellular matrix components have important regulatory functions during cell proliferation and differentiation. In recent study, extracellular matrix were shown to have a strong effect on skeletal muscle differentiation. Here, we aimed to elucidate the effects of extracellular matrix protein 2 (ECM2), an extracellular matrix component, on the differentiation of bovine skeletal muscle‐derived satellite cells (MDSCs). Western blot and immunofluorescence analyses were used to elucidate the ECM2 expression pattern in bovine MDSCs during differentiation in vitro. CRISPR/Cas9 technology was used to activate or inhibit ECM2 expression to study its effects on the in vitro differentiation of bovine MDSCs. ECM2 expression was shown to increase gradually during bovine MDSC differentiation, and the levels of this protein were higher in more highly differentiated myotubes. ECM2 activation promoted MDSC differentiation, whereas its suppression inhibited the differentiation of these cells. Here, for the first time, we demonstrated the importance of ECM2 expression during bovine MDSC differentiation; these results could lead to treatments that help to increase beef cattle muscularity.
Routine exercise testing could not predict T‐wave oversensing in a patient after a subcutaneous implantable cardioverter‐defibrillator implant
Authors: Konishi Shozo , Minamiguchi Hitoshi , Ozu Kentaro , Mizuno Hiroya , Hikoso Shungo , Yamaguchi Osamu , Sakata Yasushi
Published: December 2017

Key Clinical Message

Subcutaneous implantable cardioverter‐defibrillators (S‐ICDs) are susceptible to T‐wave oversensing (TWOS) caused by high rate‐dependent QRS–T morphology changes. We experienced an inappropriate S‐ICD shock due to TWOS, which could not be predicted by routine exercise testing. A newly available high‐pass filter might be effective for avoiding this.
Highly Dispersed Ultrafine Palladium Nanoparticles Enabled by Functionalized Porous Organic Polymer for Additive‐Free Dehydrogenation of Formic Acid
Authors: Cui Caiyan , Tang Yujiao , Ziaee Muhammad Asad , Tian Dongxu , Wang Ruihu
Published: December 2017

Formic acid (FA) is one of the most favorable chemical hydrogen storage materials for renewable energy transformation, the development of efficient heterogeneous catalysts for ultraclean H2 generation from FA in the absence of any alkalis or additives under mild conditions remains a major challenge. Here, we present a porous organic polymer containing triphenylamine (TPA) and 2,6‐bis(1,2,3‐triazol‐4‐yl)pyridyl (BTP) units (TB‐POP). The ultrafine palladium nanoparticles (NPs) with an average size of 1.5±0.6 nm can be facilely generated using convenient methods and are uniformly dispersed over the TB‐POP support. TPA and BTP units are homogeneously arranged in the host framework of TB‐POP; they serve as effective alternatives of basic sites to deprotonate FA into formate intermediates. Pd@TB‐POP has demonstrated remarkable catalytic activity and high selectivity in additive‐free dehydrogenation of aqueous FA solution. The value of initial turnover frequency (TOF) at 50 °C is as high as 1344 h−1. In sharp contrast, the use of sodium formate as an additive in the catalytic system results in the decrement of catalytic activity. The ultrafine palladium NPs are effectively immobilized during dehydrogenation of FA, and no aggregation of palladium NPs is observed after consecutive catalytic runs.
Stoichiometry‐Controlled Inversion of Supramolecular Chirality in Nanostructures Co‐assembled with Bipyridines
Authors: Wang Fang , Feng Chuan‐Liang
Published: December 2017

To control supramolecular chirality of the co‐assembled nanostructures, one of the remaining issues is how stoichiometry of the different molecules involved in co‐assembly influence chiral transformation. Through co‐assembly of achiral 1,4‐bis(pyrid‐4‐yl)benzene and chiral phenylalanine‐glycine derivative hydrogelators, stoichiometry is found to be an effective tool for controlling supramolecular chirality inversion processes. This inversion is mainly mediated by a delicate balance between intermolecular hydrogen bonding interactions and π–π stacking of the two components, which may subtly change the stacking of the molecules, in turn, the self‐assembled nanostructures. This study exemplifies a simplistic way to invert the handedness of chiral nanostructures and provide fundamental understanding of the inherent principles of supramolecular chirality.
Shape‐Persistent [4+4] Imine Cages with a Truncated Tetrahedral Geometry
Authors: Lauer Jochen C. , Zhang Wen‐Shan , Rominger Frank , Schröder Rasmus R. , Mastalerz Michael
Published: December 2017

The synthesis of shape‐persistent organic cage compounds is often based on the usage of multiple dynamic covalent bond formation (such as imines) of readily available precursors. By careful choice of the precursors geometry, the geometry and size of the resulting cage can be accurately designed and indeed a number of different geometries and sizes have been realized to date. Despite of this fact, little is known about the precursors conformational rigidity and steric preorganization of reacting functional groups on the outcome of the reaction. Herein, the influence of conformational rigidity in the precursors on the formation of a [4+4] imine cage with truncated tetrahedral geometry is discussed.
High‐Mobility Self‐Assembling Truxenone‐Based n‐Type Organic Semiconductors
Authors: Gómez‐Esteban Sandra , Benito‐Hernandez Angela , Termine Roberto , Hennrich Gunther , Navarrete Juan T. López , Ruiz Delgado M. Carmen , Golemme Attilio , Gómez‐Lor Berta
Published: December 2017

The synthesis, self‐assembly, and semiconducting properties of a series of disk‐like truxenone derivatives, functionalized with three peripheral long alkyl chains, either directly attached or distanced by linking phenyl or ethynyl groups, are reported. The strategy of distancing the alkyl chains from the central aromatic cores induces in these discotics well‐ordered columnar assemblies and has a favorable effect on their charge‐carrier mobility. Electron mobility values above 1 cm2 V−1 S−1 were determined for a truxenone functionalized with three peripheral decynyl chains by means of the space charge–limited current technique. DFT calculations help to rationalize the high mobility values found for these new truxenone‐based systems, indicating efficient intermolecular electronic couplings (fostered by a favorable stacking configuration) and moderate intramolecular reorganization energies for electrons in the origin of such high mobilities.
Wurster‐Type Nanographenes as Stable Diradical Dications
Authors: Desroches Maude , Morin Jean‐Francois
Published: December 2017

Three new and stable diradical dications based on the 4,10‐dibromoanthanthrone have been synthesized and characterized. In their dicationic state, the amines show a biradical character in the ground state. Their magnetic properties have been investigated by NMR and EPR spectroscopies. The dicationic salts shows strong and broad optical absorption in the near‐infrared region. The main driving force to obtain a ground state biradical is the high steric hindrance that prevents planarization of the diphenylamines with the anthanthrone aromatic core. The radical cations are isolated in two perpendicular π‐systems as demonstrated by X‐ray diffraction structures. This work provides a new bridging unit in the search for biradical bis(triarylamines) salts.
Chirality of 20‐membered unclosed cryptand: Macroring distortion via lariat arm modification
Authors: Jurczak Janusz , Sobczuk Adam , Dąbrowa Kajetan , Lindner Marcin , Niedbała Patryk , Stepniak Pawel
Published: December 2017

Some of 19‐membered unclosed cryptands were recognized as chiral species in a solid state. While, in terms of 20‐membered macrocycle, we tune the lariat arm, developing the synthesis of α‐ and β‐naphthyl terminated moieties to gain the structural control over chirality phenomena of these systems. Indirect synthetic approach delineates the way to reach both target structures. Solely, macrocycle functionalized with the β‐naphthyl group is capable of desirable interactions with the frame of entity inducing its stronger bending that leads to the chiral crystals formation. Their structural features were examined by single crystal X‐ray diffraction and chiroptical method, represented by ECD/UV spectroscopy.
Magnetic drug targeting simulations in blood flows with fluid‐structure interaction
Authors: Calandrini Sara , Capodaglio Giacomo , Aulisa Eugenio
Published: December 2017

We present fluid‐structure interaction simulations of magnetic drug targeting (MDT) in blood flows. In this procedure, a drug is attached to ferromagnetic particles to externally direct it to a specific target after it is injected inside the body. The goal is to minimize the healthy tissue affected by the treatment and to maximize the number of particles that reach the target location. Magnetic drug targeting has been studied both experimentally and theoretically by several authors. In recent years, computational fluid dynamics simulations of MDT in blood flows have been conducted to obtain further insight on the combination of parameters that provide the best capture efficiency. However, to this day, no computational study addressed MDT in a fluid‐structure interaction setting. With this paper, we aim to fill this gap and investigate the impact of the solid deformation on the capture efficiency.
A compartment–quasi‐3D multiscale approach for drug absorption, transport, and retention in the human lungs
Authors: Kannan Ravishekar (Ravi) , Singh Narender , Przekwas Andrzej
Published: December 2017

Most current models used for modeling the pulmonary drug absorption, transport, and retention are 0D compartmental models where the airways are generally split into the airways and alveolar sections. Such block models deliver low fidelity solutions and the spatial lung drug concentrations cannot be obtained. Other approaches use high fidelity CFD models with limited capabilities due to their exorbitant computational cost. Recently, we presented a novel, fast‐running and robust quasi‐3D (Q3D) model for modeling the pulmonary airflow. This Q3D method preserved the 3D lung geometry, delivered extremely accurate solutions, and was 25 000 times faster in comparison to the CFD methods. In this paper, we present a Q3D‐compartment multiscale combination to model the pulmonary drug absorption, transport, and retention. The initial deposition is obtained from CFD simulations. The lung absorption compartment model of Yu and Rosania is adapted to this multiscale format. The lung is modeled in the Q3D format till the eighth airway generation. The remainder of the lung along with the systemic circulation and elimination processes was modeled using compartments. The Q3D model is further adapted, by allowing for various heterogeneous annular lung layers. This allows us to model the drug transport across the layers and along the lung. Using this multiscale model, the spatiotemporal drug concentrations in the different lung layers and the temporal concentration in the plasma are obtained. The concentration profile in the plasma was found to be better aligned with the experimental findings in comparison with compartmental model for the standard test cases. Thus, this multiscale model can be used to optimize the target‐specific drug delivery and increase the localized bioavailability, thereby facilitating applications from the bench to bedside for various patient/lung‐disease variations.
3′‐O‐Caged 2′‐Deoxynucleoside Triphosphates for Light‐Mediated, Enzyme‐Catalyzed, Template‐Independent DNA Synthesis
Authors: Mathews Anu Stella , Yang Haikang , Montemagno Carlo
Published: December 2017

Synthesis, purification, and characterization of 3′‐O‐caged 2′‐deoxyribonucleoside triphosphates (dNTPs), namely 3′‐O‐(2‐nitrobenzyl)‐2′‐deoxy ribonucleoside triphosphates (NB‐dNTPs) and 3′‐O‐(4,5‐dimethoxy‐2‐nitrobenzyl)‐2′‐deoxy ribonucleoside triphosphates (DMNB‐dNTPs), are discussed in detail. A total of eight 3′‐O‐caged dNTPs are synthesized with specific protocols depending on the nitrogenous base on the first carbon, i.e., adenine, guanine, thymine, and cytosine, as well as the photo‐cleavable group, i.e, 2‐nitrobenzyl and 4,5‐ dimethoxy‐2‐nitrobenzyl, to be attached in the 3′‐O position. The purification of the synthesized compounds is done using ion‐exchange and flash chromatography; this is followed by structural confirmation by nuclear magnetic resonance (NMR) and mass spectroscopy (MS). The efficiency of the designed compounds is tested by conducting and evaluating UV‐cleaving experiments at 365 nm with proton NMR and LC‐MS curves. Finally, the application of the 3′‐O‐cagged dNTPs in template‐independent, enzyme‐catalyzed, photo‐mediated oligonucleotide synthesis is demonstrated. © 2017 by John Wiley & Sons, Inc.
Salivary intercellular adenosine triphosphate testing in primary caretakers: An examination of statistical significance versus diagnostic predictability
Authors: Bill Crystal , Danielson Judy A. , Jones Robert S.
Published: December 2017

A primary caretaker is a potential reservoir of bacteria for an infant child and can be evaluated during a child's caries risk assessment. The aim of this study was to investigate an indirect method for assessing Streptococcus mutans and Streptococcus sobrinus (MS) and lactobacillus (LB) levels in a caretaker's saliva. Thirty‐eight primary caretakers participated in the study to determine whether a 2‐step method to assess the intracellular adenosine triphosphate (ATP) levels in saliva (saliva i‐ATP method) predicted higher MS and LB levels. This method was tested against a 1‐step swab‐based total ATP testing of dental plaque (plaque t‐ATP method). Receiver operating characteristic (ROC) curves were used to examine the relationship between specificity and sensitivity of the two diagnostic tests. Although the area under the ROC curves of both the saliva i‐APT (0.823) and the plaque t‐ATP (0.774) methods were shown to be statistically different (p < .05) than the null hypothesis test of a random coin flip, the diagnostic predictability of the ATP tests to assess high levels of MS and LB remained low. The optimal cutoff, which was defined by the Youden index, for the saliva i‐ATP method produced a sensitivity/specificity of 60.7/100.0 for MS and 78.6/88.9 for LB. Applying these results to populations of low or high bacterial level prevalence produced undesirable positive and negative predictive values for future potential patients. A pair‐wise comparison of both area under the ROC curve values of the saliva i‐ATP and plaque t‐ATP did not find a statistically significant difference in using one test over the other (MS, p = .629; LB, p = .737). The findings of this study can educate dental clinicians that diagnostic tests, such as the 2‐step saliva i‐ATP method, can be found to be statistically significant but not ideal for patient use in terms of diagnostic predictability.
Calculating individualized glycaemic targets using an algorithm based on expert worldwide diabetologists: Implications in real‐life clinical practice
Authors: Alvarez‐Guisasola Fernando , Cebrián‐Cuenca Ana M. , Cos Xavier , Ruiz‐Quintero Manuel , Millaruelo Jose M. , Cahn Avivit , Raz Itamar , Orozco‐Beltrán Domingo ,   on behalf of the Spanish Society of Family Medicine Diabetes Group
Published: December 2017

Background

The aim of this study was to assess the clinical implications of calculating an individualized HbA1c target using a recently published algorithm in a real‐life clinical setting.

Methods

General practitioners (GPs) from the Spanish Society of Family Medicine Diabetes Expert Group were invited to participate in the study. Each GP selected a random sample of patients with diabetes from his or her practice and submitted their demographic and clinical data for analysis. Individualized glycaemic targets were calculated according to the algorithm. Predictors of good glycaemic control were studied. The rate of patients attaining their individualized glycaemic target or the uniform target of HbA1c < 7.0% was calculated.

Results

Forty GPs included 408 patients in the study. Of the 8 parameters included in the algorithm, “comorbidities,” “risk of hypoglycaemia from treatment,” and “diabetes duration” had the greatest impact on determining the individualized glycaemic target. Number of glucose‐lowering agents and adherence were independently associated with glycaemic control. Overall, 60.5% of patients had good glycaemic control per individualized target, and 56.1% were well controlled per the uniform target of HbA1c < 7.0% (P = .20). However, 12.8% (23 of 246) of the patients with HbA1c ≥ 7.0% were adequately controlled per individualized target, and 2.6% (6 of 162) of the patients with HbA1c < 7.0% were uncontrolled since their individualized target was lower.

Conclusions

In a real‐life clinical setting, applying individualized targets did not change the overall rate of patients with good glycaemic control yet led to reclassification of 7.1% (29 of 408) of the patients. More studies are needed to validate these results in different populations.
Co‐morbidities in Chinese children with attention deficit/hyperactivity disorder and reading disabilities
Authors: Wang Li‐Chih , Chung Kevin Kien Hoa
Published: December 2017

The co‐morbidity of attention deficit/hyperactivity disorder (ADHD) and reading disorder (RD) is more frequent than expected. This investigation assessed the potential uniqueness of the co‐morbidity of ADHD and RD and extended existing findings to the Chinese language. A parallel group design with a post hoc analysis of group differences was employed to compare 4 groups of children (30 with ADHD, 33 with RD, 28 with ADHD + RD, and 30 typically developing) regarding their reading comprehension, attention, reading‐related abilities, and cognitive abilities. The findings indicated that children with RD and/or ADHD symptom(s) exhibited diverse cognitive profiles, and the distinguishing factor contributed to different inhibitions. Additionally, Chinese‐speaking children with the co‐morbid symptoms of RD and ADHD demonstrated greater deficits in auditory working memory and rapid naming than did the pure‐deficit groups. Furthermore, although problems with phonological awareness were similar between the 2 groups, the deficiency of orthographic knowledge was more severe in children with RD than in the co‐morbid group. The ADHD + RD group's cognitive and reading‐related abilities displayed a relatively complicated pattern that should be considered in the diagnosis of either RD or ADHD and their remediation design.
Rapid and Simultaneous Determination of the Iodine Value and Saponification Number of Edible Oils by FTIR Spectroscopy
Authors: Xu Lirong , Zhu Xufei , Yu Xiuzhu , Huyan Zongyao , Wang Xingguo
Published: December 2017

A rapid method is developed to facilitate the Fourier transform infrared (FTIR) spectroscopy analysis of edible oils using disposable polyethylene (PE) films as sample support for the determination of the iodine value (IV) and saponification number (SN). For direct IV analysis, quantification is achieved using the cis and trans double band region (3206–2992 cm−1) by a partial least squares calibration model, whereas, SN is directly determined using the area in carbon chain skeleton vibration absorption region (781–650 cm−1). The proposed method is applicable to various edible oils ranging in IV from 7.0 to 190.0 g 100 g−1 and SN from 162.7 to 222.0 mg g−1 with good precision and accuracy (relative standard deviations 0.39 and 0.32%, respectively) relative to the AOCS standard methods but with markedly less sample preparation and analytical effort.

Practical Applications: Standard titration methods for determining the IV and SN of edible oils are labor intensive and require complex solvents and reagents. The PE‐film‐based FTIR method is more sensitive than attenuated total reflectance‐FTIR method and free from problems associated with the viscosity of oils, which is practical and easy to operate. The method can further simplify and facilitate simultaneous FTIR IV and SN analyses and is applicable to various edible oils over a wide range.

A PE‐film‐based FTIR method is developed to determine the iodine value (IV) and saponification number (SN) of edible oils. The regions 3206–2992 cm−1 and 781–650 cm−1 are selected for IV and SN analysis, respectively. In the graphical abstract the IV and SN calibration and validation figures are presented.
Copper‐Catalyzed Tandem Reaction of Enamino Esters with ortho‐Halogenated Aromatic Carbonyls: One‐Pot Approach to Functionalized Quinolines
Authors: Peng Fei , Liu Jin , Li Lili , Chen Zhiwei
Published: December 2017

An efficient and practical approach for the synthesis of functionalized quinolines has been developed by using the copper‐catalyzed tandem C–C bond formation and C–N coupling reaction of enamino esters and ortho‐halogenated aromatic carbonyl compounds. Various functional groups were tolerated under the reaction conditions, and a series of quinolines were easily obtained in moderate to good yields. A gram‐scale reaction was also performed to demonstrate a further application of this synthetic method.
Soft and Hard Piezoelectric Ceramics and Single Crystals for Random Vibration Energy Harvesting
Authors: Shahab Shima , Zhao Sihong , Erturk Alper
Published: December 2017

Vibration‐based energy harvesting for enabling next‐generation self‐powered devices is a rapidly growing research area. In real‐world applications, the ambient vibrational energy is often available in non‐deterministic forms rather than the extensively studied deterministic scenarios, such as simple harmonic excitation. It is of interest to choose the best piezoelectric material for a given random excitation. Here, performance comparisons of various soft and hard piezoelectric ceramics and single crystals are presented for electrical power generation under band‐limited off‐resonance and wideband random vibration energy‐harvesting scenarios. For low‐frequency off‐resonance excitation, it is found that soft piezoelectric ceramics based upon lead zirconate titanate (e.g., PZT‐5H and PZT‐5A) outperform their hard counterparts (e.g., PZT‐4 and PZT‐8), and likewise soft single crystals based upon lead magnesium niobate and lead titanate as well as PZT (e.g., PMN‐PT and PMN‐PZT) outperform the relatively hard ones (e.g., manganese‐doped PMN‐PZT‐Mn). Overall, for such off‐resonance random vibrations, PMN‐PT is the most suitable choice among the materials studied. For wideband random excitation with a bandwidth covering the fundamental resonance of the harvester, hard piezoelectric ceramics offer larger power output compared to soft ceramics, and likewise hard single crystals produce larger power compared to their soft counterparts. Remarkably, a hard piezoelectric ceramic (e.g., PZT‐8) can outperform a soft single crystal (e.g., PMN‐PT) for wideband random vibration energy harvesting.
Influence of Impregnation Processes on Ruthenium–Molybdenum Carbon Catalysts for Selective Hydrodeoxygenation of Biomass‐Derived Sorbitol into Renewable Alkanes
Authors: Weng Yujing , Wang Tiejun , Duan Peigao , Wang Chenguang , Wang Feng , Liu Qiying , Chen Lungang , Wang Haiyong , Liang Zheng , Ma Longlong
Published: December 2017

Sorbitol, as a C6 sugar related compound derived from cellulose, is regarded as a promising biomass‐derived substrate and has characteristically higher oxygen content than in fossil‐based resources. In this work, ruthenium–molybdenum carbon catalysts prepared by different impregnation processes were employed and extensively studied in a trickle‐bed reactor for sorbitol hydrodeoxygenation (HDO). Interestingly, these catalysts afforded remarkably different HDO performance. Ruthenium–molybdenum catalysts prepared by ultrasonic treatment and calcination obtained high HDO performance in sorbitol conversion with 79.8 % carbon yield of C5/C6 alkanes (pentane and hexane), almost twice that of ruthenium–molybdenum catalysts prepared without using a calcination processes. Therefore, a series of characterization studies (N2‐adsorption, XRD, HRTEM, XPS, H2‐TPR, CO‐TPD, NH3‐TPD, Py‐IR spectra, etc.) were performed over relevant catalysts to study the catalytic mechanism. The results suggest that prior calcination offers a better chance for the proximity between Ru and Mo precursors to produce the bimetallic catalytic structure Ru–MoOx, which produces high HDO performance.
Strong variation in weathering of layered rock maintains hillslope‐scale strength under high precipitation
Authors: Von Voigtlander Jennifer , Clark Marin K. , Zekkos Dimitrios , Greenwood William W. , Anderson Suzanne P. , Anderson Robert S. , Godt Jonathan W.
Published: December 2017

The evolution of volcanic landscapes and their landslide potential are both dependent upon the weathering of layered volcanic rock sequences. We characterize critical zone structure using shallow seismic Vp and Vs profiles and vertical exposures of rock across a basaltic climosequence on Kohala peninsula, Hawai’i, and exploit the dramatic gradient in mean annual precipitation (MAP) across the peninsula as a proxy for weathering intensity. Seismic velocity increases rapidly with depth and the velocity–depth gradient is uniform across three sites with 500–600 mm/yr MAP, where the transition to unaltered bedrock occurs at a depth of 4 to 10 m. In contrast, velocity increases with depth less rapidly at wetter sites, but this gradient remains constant across increasing MAP from 1000 to 3000 mm/yr and the transition to unaltered bedrock is near the maximum depth of investigation (15–25 m). In detail, the profiles of seismic velocity and of weathering at wet sites are nowhere monotonic functions of depth. The uniform average velocity gradient and the greater depths of low velocities may be explained by the averaging of velocities over intercalated highly weathered sites with less weathered layers at sites where MAP > 1000 mm/yr. Hence, the main effect of climate is not the progressive deepening of a near‐surface altered layer, but rather the rapid weathering of high permeability zones within rock subjected to precipitation greater than ~1000 mm/yr. Although weathering suggests mechanical weakening, the nearly horizontal orientation of alternating weathered and unweathered horizons with respect to topography also plays a role in the slope stability of these heterogeneous rock masses. We speculate that where steep, rapidly evolving hillslopes exist, the sub‐horizontal orientation of weak/strong horizons allows such sites to remain nearly as strong as their less weathered counterparts at drier sites, as is exemplified by the 50°–60° slopes maintained in the amphitheater canyons on the northwest flank of the island. Copyright © 2017 John Wiley & Sons, Ltd.