bluuebunny/crossref_metadata_2025_split huggingface dataset:
Optimization of lipase‐catalyzed polymerization of benzyl malolactonate through a design of experiment approach
Authors: Casajus Hubert , Tranchimand Sylvain , Wolbert Dominique , Nugier‐Chauvin Caroline , Cammas‐Marion Sandrine 
Published: November 2016

ABSTRACTPolyesters are polymers of choice in the design of drug delivery systems as a result of their good biocompatibility and their (bio)degradability. Such polyesters are mainly obtained by polymerization techniques using chemically based initiators whose presence in the final materials, even at trace levels, might induce toxic effects on in vivo uses. Therefore, lipases‐catalyzed ring opening polymerization (ROP) of lactones might be considered as interesting solutions. In this context, we have studied the possibilities to use lipase‐catalyzed ROP of the benzyl malolactonate (MLABe) to obtain the poly(benzyl malate), PMLABe. A Design of Experiment (DoE) approach has been elaborated to identify the important parameters having a significant influence on the polymerization reaction and on the characteristics of the obtained PMLABe. Such DoE technique allowed us to select conditions for lipase‐catalyzed ROP of MLABe leading to PMLABe with a mass‐average molar mass of around 10,000 g/mol with a dispersity of 1.4. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44604.
Locomotor Hand Postures, Carpal Kinematics During Wrist Extension, and Associated Morphology in Anthropoid Primates
Authors: Orr Caley M. 
Published: November 2016

ABSTRACTThe biomechanics of wrist extension (or dorsiflexion) are important for understanding functional adaptation of the primate hand because extension mobility varies with habitual locomotor hand posture and facilitates certain manipulative tasks. Here, intercarpal kinematics are employed to investigate mechanisms underlying wrist extension in a sample of anthropoids representing various arboreal and terrestrial locomotor modes. Carpal kinematics are studied using computed‐tomography of cadaveric forelimbs, and these data are combined with a morphometric analysis of biomechanically‐informative anatomical features. The results indicate that stiff‐wristed knuckle‐walking chimpanzees and digitigrade baboons are characterized by low ranges of motion (ROMs) at the radiocarpal and midcarpal complexes. Palmigrade‐capable monkeys have high extension ROMs at both the radiocarpus and midcarpus, while palmigrade‐capable orangutans achieve wrist extension through moderate radiocarpal ROMs and high midcarpal ROMs. Morphometrics demonstrate that a more projecting dorsal ridge of the distal radius corresponds with low‐to‐moderate radioscaphoid mobility in the apes, but that baboons resemble palmigrade‐capable monkeys in this metric. Thus, the dorsal ridge of the radius alone is not a good indicator of wrist mobility and hand posture. However, the extent of the lunate's articular arc on the dorsum of the capitate head is correlated with midcarpal mobility across taxa. These findings suggest that although a precise relationship between wrist extension ROM and morphology is difficult to define, the presence of a pronounced dorsal ridge combined with an abbreviated dorsal capitate articular arc reflects limited overall dorsiflexion with attendant constraints on the adoption of palmigrade hand postures. Anat Rec, 300:382–401, 2017. © 2016 Wiley Periodicals, Inc.
Brief Report: Partial‐ and Full‐Thickness Focal Cartilage Defects Contribute Equally to Development of New Cartilage Damage in Knee Osteoarthritis: The Multicenter Osteoarthritis Study
Authors: Guermazi Ali , Hayashi Daichi , Roemer Frank W. , Niu Jingbo , Quinn Emily K. , Crema Michel D. , Nevitt Michael C. , Torner James , Lewis Cora E. , Felson David T. 
Published: November 2016

ObjectiveTo determine the risk of incident cartilage damage at follow‐up in subregions that are undamaged at baseline, by comparing tibiofemoral joint compartments with a baseline focal partial‐thickness or full‐thickness cartilage defect against compartments without any baseline cartilage damage, in knees with and those without radiographic osteoarthritis (OA).MethodsWe included participants in the Multicenter Osteoarthritis Study for whom there were semiquantitative magnetic resonance imaging readings at baseline and at 30 months. We estimated the risk of incident cartilage defects developing in tibiofemoral compartments with prevalent partial‐thickness and full‐thickness cartilage defects in only one subregion within the compartment, using tibiofemoral compartments with no baseline cartilage defects as a referent. Logistic regression with generalized estimating equations was used for all analyses, with adjustments for confounders.ResultsA total of 374 compartments (359 knees) were included, and 140 knees (39%) had radiographic OA. Compared to compartments with no baseline cartilage defects, those with partial‐thickness (adjusted odds ratio 1.62 [95% confidence interval 1.06–2.47]) and full‐thickness (adjusted odds ratio 1.92 [95% confidence interval 1.00–3.66]) cartilage defects in a subregion had a higher risk of incident cartilage defects in other subregions in the same compartment.ConclusionPrevalent focal cartilage defects, regardless of defect depth, in a single subregion within a tibiofemoral joint compartment increase the risk of developing new cartilage damage in other subregions of the same compartment for middle‐aged to elderly persons with or at high risk of knee OA.
Regulation of Chondrocyte Survival in Mouse Articular Cartilage by p63
Authors: Taniguchi Yuki , Kawata Manabu , Ho Chang Song , Mori Daisuke , Okada Keita , Kobayashi Hiroshi , Sugita Shurei , Hosaka Yoko , Inui Hiroshi , Taketomi Shuji , Yano Fumiko , Ikeda Toshiyuki , Akiyama Haruhiko , Mills Alea A. , Chung Ung‐il , Tanaka Sakae , Kawaguchi Hiroshi , Saito Taku 
Published: November 2016

ObjectiveTranscription factor p63, of the p53 family, regulates cell proliferation, survival, and apoptosis in various cells and tissues. This study was undertaken to examine the expression and roles of p63 transcript variants in the mouse growth plate and articular chondrocytes.MethodsFor in vivo analyses, we generated Cre‐mediated TAp63α‐transgenic and TAp63γ‐transgenic mice. To induce tissue‐specific overexpression or deletion in chondrocytes, chondroprogenitor cells, or early limb bud mesenchymal cells, we used Col2a1‐Cre, Sox9‐Cre, and Prx1‐Cre mice, respectively. We analyzed osteoarthritis (OA) development with aging or surgically induced instability in Prx1‐Cre;p63fl/fl (P–conditional knockout) mice.ResultsAmong major variants, TAp63α and TAp63γ are highly expressed in mouse primary costal and articular chondrocytes. The p63 protein was predominantly localized in the hypertrophic zone of the embryonic limb cartilage, and in the middle zone of articular cartilage. No obvious change was observed in skeletal growth of TAp63α‐transgenic mice, Sox9‐Cre;p63fl/fl, or P–conditional knockout mice, while that of TAp63γ‐transgenic mice was impaired due to ectopic apoptosis and the resulting decreased number of chondrocytes. Expression of proapoptotic genes including bax, noxa, puma, and fas was increased in TAp63γ‐transgenic mouse chondrocytes, and their transcription was probably sustained by p53 in p63–conditional knockout mouse chondrocytes because both proteins were coexpressed in the growth plate. In contrast, p53 was expressed in the superficial zone of articular cartilage, differently from p63. Notably, P–conditional knockout mice showed significant resistance to OA development, with suppression of chondrocyte apoptosis in the aging and surgical models.ConclusionWe demonstrated regulation of chondrocyte survival in articular cartilage by p63.
“Patients with amyotrophic lateral sclerosis (ALS) are usually nice persons”—How physicians experienced in ALS see the personality characteristics of their patients
Authors: Mehl Theresa , Jordan Berit , Zierz Stephan 
Published: November 2016

AbstractIntroductionPhysicians experienced in the treatment of patients with amyotrophic lateral sclerosis (ALS) occasionally describe these patients as “nice” persons.MethodsALS experienced physicians (n = 36) were asked to assess the personality characteristics of ALS patients using a multidimensional personality questionnaire based on the five‐factor model of personality. Control groups consisted of physicians experienced in Myasthenia gravis (MG) (n = 21) and lung cancer (LC) (n = 36).ResultsIn the dimension Agreeableness ALS patients were rated significantly higher than the other groups (p < .001). This was mainly due to the high scores for converse adjective pairs “stubborn—compliant” and “selfish—helpful”.DiscussionThe dimension Agreeableness is very similar to “niceness”. Results support the anecdotal description of ALS patients as “nice” persons. Personality characteristics of ALS patients differentiate them from other patient groups. It remains open whether the “nice” personality structure is linked to the susceptibility to the disease.
Superior Catalytic Performance of Hierarchically Micro‐Meso‐Macroporous CuAlPO‐5 for the Oxidation of Aromatic Amines under Mild Conditions
Authors: Ke Qingping , Wu Mingzhou , Yu Huizhen , Lu Guanzhong 
Published: November 2016

AbstractAromatic nitro compounds are versatile building blocks for organic synthesis because of easy transformation of the nitro group into other diverse functional groups. Herein, hierarchical mesoporous–macroporous CuAlPO‐5 was prepared and found to exhibit excellent catalytic activity and stability for the oxidation of aromatic amines to nitroarenes. For the oxidation of bulky aromatic amine molecules (e.g., 1‐naphthalenamine), hierarchical CuAlPO‐5 exhibited higher selectivity to the product than homogeneous Cu catalysts and higher catalytic activity than traditional microporous CuAlPO‐5; the former was attributed to shape selectivity to the product and the latter was attributed to improved diffusion of bulky molecules inside the meso‐ and macropores. After CuAlPO‐5 was used five times in the oxidation of 4‐bromoaniline, >98.6 % conversion and 98.1 % selectivity to the product were obtained. This shows the potential and attractiveness of this method for the preparation of nitroarenes by the selective oxidation of organic amines.
Liquid‐to‐Particle Mass Transfer in a Structured‐Bed Minireactor
Authors: Templis Chrysovalantis C. , Papayannakos Nikos G. 
Published: November 2016

AbstractLiquid‐to‐particle mass transfer effects in a string pellet minireactor were studied by applying the diffusion‐controlled copper dissolution technique. Structured beds were formed with cylindrical particles in spiral and vertical configurations and operated with liquid and gas‐liquid feeds in upflow mode. Single‐ and two‐phase flow experiments were conducted to study the effects of the gas and the liquid superficial velocities on the liquid‐to‐particle mass transfer coefficient. Computational fluid dynamics calculations were performed to study the effect of the arrangement of the particles in the reactor tube on the liquid‐to‐particle effective mass transfer coefficient for the single‐phase flow. Correlations of the mass transfer coefficient with the operating conditions were derived.
d‐ Versus l‐Glucose Conjugation: Mitochondrial Targeting of a Light‐Activated Dual‐Mode‐of‐Action Ruthenium‐Based Anticancer Prodrug
Authors: Lameijer Lucien N. , Hopkins Samantha L. , Brevé Tobias G. , Askes Sven H. C. , Bonnet Sylvestre 
Published: November 2016

AbstractLight‐activated ruthenium polypyridyl anticancer prodrugs often suffer from poor water solubility, poor selectivity, and/or ill‐defined intracellular targets. Coordination of the d‐ or l‐glucose thioether ligand 3 (2‐(2‐(2‐(methylthio)ethoxy)ethoxy)ethyl‐β‐glucopyranoside) to the highly lipophilic ruthenium complex [Ru(tpy)(dppn)(H2O)]2+ ([1]2+; dppn=benzo[i]dipyrido‐[3,2‐a:2′,3′‐c]phenazine, tpy=2,2′:6′,2′′‐terpyridine) solved all these problems at once. The two enantiomers of [Ru(tpy)(dppn)(3)][PF6]2, [d‐2][PF6]2 and [l‐2][PF6]2, were soluble in water, which allowed the influence of the chirality of the glucose moiety on uptake, toxicity, and intracellular localization of the prodrug to be probed without changing any other physicochemical properties. Both compounds showed mild, but different, cytotoxicity in A549 (human lung carcinoma) and MCF‐7 (human breast adenocarcinoma) cancer cells in the dark, whereas following low doses of visible light irradiation (3.1 J cm−2 at λ = 454 nm), a similar, but high cytotoxicity (EC50 < 1 μm), was observed. Irrespective of the chirality, both slightly emissive Ru complexes were found in the mitochondria, and two modes of action may contribute to light‐induced cell death: 1) the glucose thioether ligand is photosubstituted by water, thus [1]2+, which interacts with DNA at an exceptionally high 400:1 base pair/Ru ratio, is released; 2) both [1]2+ and [2]2+ produce massive amounts of singlet oxygen, which leads to very efficient photodynamic DNA cleavage.
Study of (Cyclic Peptide)–Polymer Conjugate Assemblies by Small‐Angle Neutron Scattering
Authors: Koh Ming Liang , FitzGerald Paul A. , Warr Gregory G. , Jolliffe Katrina A. , Perrier Sébastien 
Published: November 2016

AbstractWe present a fundamental study into the self‐assembly of (cyclic peptide)–polymer conjugates as a versatile supramolecular motif to engineer nanotubes with defined structure and dimensions, as characterised in solution using small‐angle neutron scattering (SANS). This work demonstrates the ability of the grafted polymer to stabilise and/or promote the formation of unaggregated nanotubes by the direct comparison to the unconjugated cyclic peptide precursor. This ideal case permitted a further study into the growth mechanism of self‐assembling cyclic peptides, allowing an estimation of the cooperativity. Furthermore, we show the dependency of the nanostructure on the polymer and peptide chemical functionality in solvent mixtures that vary in the ability to compete with the intermolecular associations between cyclic peptides and ability to solvate the polymer shell.
Fluorogenic Behaviour of the Hetero‐Diels–Alder Ligation of 5‐Alkoxyoxazoles with Maleimides and their Applications
Authors: Renault Kévin , Jouanno Laurie‐Anne , Lizzul‐Jurse Antoine , Renard Pierre‐Yves , Sabot Cyrille 
Published: November 2016

AbstractFluorogenic reactions are largely underrepresented in the toolbox of chemoselective ligations despite their tremendous potential, particularly in chemical biology and biochemistry. In this respect, we have investigated in full detail the fluorescence behaviour of the azaphthalamide, a scaffold which is generated through a hetero‐Diels–Alder reaction of 5‐alkoxyoxazole and maleimide derivatives under mild conditions that are compatible with, among others, peptide chemistry. The scope and limitations of such a fluorogenic labelling strategy were examined through four distinct applications, which target enzymatic activities or bioorthogonal reactions.
The Design, Synthesis, and Evaluation of 1,5,7‐Trisubstituted‐3‐Pyridyl‐Xanthones for Use as Insecticides Starting from Pyripyropene A
Authors: Fuse Shinichiro , Matsumura Keisuke , Johmoto Kohei , Uekusa Hidehiro , Tanaka Hiroshi , Hirose Tomoyasu , Sunazuka Toshiaki , Ōmura Satoshi , Takahashi Takashi 
Published: November 2016

AbstractA readily accessible template of 1,5,7‐trisubstituted‐3‐pyridyl‐xanthones was designed starting from naturally occurring pyripyropene A for agrichemical development. Our originally developed Ag2CO3‐mediated oxidative cyclization enabled ready access to the key scaffold, 1,5,7‐trihydroxy‐3‐chloro‐xanthone. The chemo‐ and regioselective sequential introduction of four substituents to the scaffold rapidly afforded the desired, structurally diverse 1,5,7‐trisubstituted‐3‐pyridyl‐xanthones. An evaluation of insecticidal activity revealed that one of the synthesized compounds retained insecticidal activity against vetch aphid and green peach aphid. The observed insecticidal spectrum was similar to that of pyripyropene A. The developed template could be a valuable aid for future agrichemical development.
Synthesis of Structurally Varied 1,3‐Disiloxanediols and Their Activity as Anion‐Binding Catalysts
Authors: Diemoz Kayla M. , Wilson Sean O. , Franz Annaliese K. 
Published: November 2016

AbstractA series of new 1,3‐disiloxanediols has been synthesized, including naphthyl‐substituted and unsymmetrical siloxanes, and demonstrated as a new class of anion‐binding catalysts. In the absence of anions, diffusion‐ordered spectroscopy (DOSY) displays self‐association of 1,3‐disiloxanediols through hydrogen‐bonding interactions. Binding constants determined for 1,3‐disiloxanediol catalysts indicate strong hydrogen‐bonding and anion‐binding abilities with unsymmetrical siloxanes displaying different hydrogen‐bonding abilities for each silanol group.
Single Heteroatom Substitutions in the Efavirenz Oxazinone Ring Impact Metabolism by CYP2B6
Authors: Cox Philip M. , Bumpus Namandjé N. 
Published: November 2016

AbstractPreviously, we observed that the oxazinone ring is important for cytochrome P450 2B6 (CYP2B6) activity toward efavirenz ((4S)‐6‐chloro‐4‐(2‐cyclopropylethynyl)‐1,4‐dihydro‐4‐(trifluoromethyl)‐2H‐3,1‐benzoxazin‐2‐one), a CYP2B6 substrate used to treat HIV. To further understand the structural characteristics of efavirenz that render it a CYP2B6 substrate, we tested the importance of each heteroatom of the oxazinone ring. We assembled a panel of five analogues: 6‐chloro‐4‐(2‐cyclopropylethynyl)‐1,4‐dihydro‐2‐methyl‐4‐(trifluoromethyl)‐2H‐3,1‐benzoxazine (1), (4S)‐6‐chloro‐4‐[(1E)‐2‐cyclopropylethenyl]‐3,4‐dihydro‐4‐(trifluoromethyl)‐2(1H)‐quinazolinone (2), (4S)‐6‐chloro‐4‐(2‐cyclopropylethynyl)‐3,4‐dihydro‐4‐(trifluoromethyl)‐2(1H)‐quinazolinone (3), 6‐chloro‐4‐(cyclopropylethynyl)‐3,4‐dihydro‐4‐(trifluoromethyl)‐2(1H)‐quinolinone (4), and 6‐chloro‐4‐(cyclopropylethynyl)‐4‐(trifluoromethyl)‐4H‐benzo[d][1,3]dioxin‐2‐one (5). The metabolism of compounds 1–5 was investigated using human liver microsomes, individual P450s, and mass spectrometry or UV/Vis absorbance detection. Steady‐state analysis of CYP2B6 metabolism of 1–5 showed KM values ranging from 0.3‐ to 3.9‐fold different from that observed for efavirenz (KM: 3.6±1.7 μm). The lowest KM values, approximating 1 μm, were observed for the metabolism of 1, whereas the greatest KM value, 14±6.4 μm, was found for 4. Our work reveals that analogues with heteroatom changes in the oxazinone ring are still CYP2B6 substrates, although the changes in KM suggest altered substrate binding.
Investigation of Methane Oxidation Reactions Over a Dual‐Bed Catalyst System using 18O Labelled DRIFTS coupling
Authors: Richard Melissandre , Duprez Daniel , Bion Nicolas , Can Fabien 
Published: November 2016

AbstractLow loading Pd‐supported (0.2 wt % Pd) Y‐stabilized zirconia (YSZ) and LaMnO3 (LM) perovskite were associated to study the partial oxidation of methane using labelled 18O2 in the gas phase. Synthesis gas production was demonstrated to occur through an indirect reaction in which oxygen is first consumed in the total methane combustion. A Mars–van Krevelen mechanism was observed over Pd/YSZ at 425 °C to yield C16O2 and C16O. A significant enhancement of the Pd/YSZ catalyst activity was achieved by the association of LM–Pd/YSZ in a dual catalyst bed, resulting in a significant increase of the oxidation rate. Vibration bands of adsorbed formate species, assumed to be intermediates to the gas production, were observed by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) coupling experiments. It was proposed that LM enables the generation of highly active singlet O2, which is activated on the YSZ oxygen vacancies to assist a rapid recovery of surface PdO and increase formate decomposition into CO and H2 in Pd‐supported catalyst.
The Planktonic Relationship Between Fluid‐Like Electrodes and Bacteria: Wiring in Motion
Authors: Tejedor‐Sanz Sara , Quejigo Jose Rodrigo , Berná Antonio , Esteve‐Núñez Abraham 
Published: November 2016

AbstractWe have explored a new concept in bacteria‐electrode interaction based on the use of fluid‐like electrodes and planktonic living cells. We show for the first time that living in a biofilm is not a strict requirement for Geobacter sulfurreducens to exchange electrons with an electrode. The growth of planktonic electroactive G. sulfurreducens could be supported by a fluid‐like anode as soluble electron acceptors and with electron transfer rates similar to those reported for electroactive biofilms. This growth was maintained by uncoupling the charge (catabolism) and discharge (extracellular respiration) processes of the cells. Our results reveal a novel method to culture electroactive bacteria in which every single cell in the medium could be instantaneously wired to a fluid‐like electrode. Direct extracellular electron transfer is occurring but with a new paradigm behind the bacteria–electrode interaction.
One‐Component Aluminum(heteroscorpionate) Catalysts for the Formation of Cyclic Carbonates from Epoxides and Carbon Dioxide
Authors: Martínez Javier , Castro‐Osma José A. , Alonso‐Moreno Carlos , Rodríguez‐Diéguez Antonio , North Michael , Otero Antonio , Lara‐Sánchez Agustín 
Published: November 2016

AbstractNew neutral and zwitterionic chiral NNO‐donor scorpionate ligands 1 and 2 were designed to obtain new mononuclear and dinuclear NNO‐heteroscorpionate aluminum complexes. Reaction of 1 with [AlR3] (R=Me, Et) in a 1:1 or 1:2 molar ratio afforded the neutral mononuclear alkyl complexes [AlR2(κ2‐bpzappe)] {R=Me (3), Et (4); bpzappeH=2,2‐bis(3,5‐dimethylpyrazol‐1‐yl)‐1‐[4‐(dimethylamino)phenyl]‐1‐phenylethanol} and bimetallic complexes [{AlR2(κ2‐bpzappe)}(μ‐O){AlR3}] [R=Me (5), Et (6)]. By reaction of complexes 3–6 with PhCH2Br, mononuclear and dinuclear cationic aluminum complexes [AlR2(κ2‐bbpzappe)]Br {R=Me (7), Et (8); bbpzappeH=N‐benzyl‐4‐[2,2‐bis(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)‐1‐hydroxy‐1‐phenylethyl]‐N,N‐dimethylbenzenaminium bromide} and [{AlR2(κ2‐bbpzappe)}(μ‐O){AlR3}]Br [R=Me (9), Et (10)] were synthesized. Both neutral aluminum complexes in the presence of Bu4NBr and cationic aluminum complexes were investigated as catalysts for cyclic carbonate formation from epoxides and carbon dioxide. Amongst them, complex 10 was found to be an efficient one‐component catalyst for the synthesis of cyclic carbonates from both monosubstituted and internal epoxides and was shown to have broad substrate scope.
Facile one‐pot preparation of a novel imidazolium‐based monolith by thiol–ene click chemistry for capillary liquid chromatography
Authors: Zhang Peng , Yang Haiguan , Chen Tao , Qin Yuemei , Ye Fanggui 
Published: November 2016

AbstractIn this work, a novel imidazolium‐based monolith was fabricated through a simple route. With 1‐vinyl‐3‐octadecylimidazolium bromide and ethylene dimethacrylate as monomers, pentaerythritol tetra‐(3‐mercaptopropionate) as crosslinker, AIBN as thermal initiator, the monolith was facilely fabricated by one‐pot thiol–ene click chemistry. The influences of both the content of monomer/crosslinker and porogenic systems on the morphology, and permeability of the monolith were studied. The optimal reaction conditions were used to prepare a homogeneous and permeable monolith. The optimal preparation of monolithic column was characterized by scanning electron microscopy, Fourier transform infrared spectrometry, X‐ray photoelectron spectroscopy, and thermogravimetric analysis. High efficiency and quick separation of alkylbenzenes, styrene and ethylbenzene, polycyclic aromatic hydrocarbon, phenols, anilines, and aromatic acids were achieved. The minimum plate height of this monolith were determined as 11.42 μm for thiourea and 13.26 μm for benzene. All results indicated that thiol–ene click chemistry provides a quick way for the fabrication of imidazolium‐based monolith.