bluuebunny/crossref_metadata_2025_split huggingface dataset:
Real‐World Experience and Impact of Canakinumab in Cryopyrin‐Associated Periodic Syndrome: Results From a French Observational Study
Authors: Kone‐Paut I. , Quartier P. , Fain O. , Grateau G. , Pillet P. , Le Blay P. , Bonnet F. , Despert V. , Stankovic‐Stojanovic K. , Willemin L. , Quéré S. , Reigneau O. , Hachulla E. 
Published: September 2016

ObjectiveThe ENVOL study was designed to assess the psychosocial impact of disease and therapy in a French cohort of cryopyrin‐associated periodic syndromes (CAPS) patients (and caregivers) treated with canakinumab.MethodsThe ENVOL study was a multicenter, observational study of CAPS patients given ≥1 canakinumab dose. Data were collected before treatment, at 6 and 12 months afterward, and at the last visit. Patients and caregivers completed questionnaires assessing changes from the 12 months of pretreatment to 12 months prior to interview. Data were analyzed retrospectively.ResultsThe study included 10 physicians and 68 patients (53 adults, 15 children). Sixty‐five patients (95.6%) were still receiving canakinumab at the last visit (median 5 years after starting therapy). The mean ± SD score for patient‐reported general health increased from 7 ± 2.9 before canakinumab to 2.7 ± 2.7 after treatment (P < 0.001). Physical and emotional symptoms resolved or improved in a substantial proportion of patients, including bodily pain (38 of 46 patients), fever (32 of 39), skin disease (35 of 41), fatigue (31 of 47), self‐confidence (29 of 46), and energy (34 of 47). Social activity, relationships, sexuality, and energy measures improved in >40% of respondents. Caregivers spent a median of 3 versus 0.5 hours/week on care in the 12 months of pretreatment versus 12 months prior to interview (P < 0.001). Following treatment, patients required fewer consultations with general practitioners (mean ± SD per patient per year: 5.2 ± 7.4 versus 8.5 ± 7.2 pretreatment), internists/rheumatologists/dermatologists (2.0 ± 2.1 versus 3.7 ± 3.9), and pediatricians (1.8 ± 1.5 versus 4.4 ± 4.2).ConclusionLong‐term treatment with canakinumab achieves a highly relevant improvement in the physical, emotional, and social lives of patients with CAPS, accompanied by a marked reduction in support required from caregivers and in health care consultations.
Relationship Between Knee Pain and Patient Preferences for Joint Replacement: Health Care Access Matters
Authors: Vina Ernest R. , Ran Di , Ashbeck Erin L. , Kaur Manjinder , Kwoh C. Kent 
Published: September 2016

ObjectiveTo determine if severity of osteoarthritis‐related knee pain is associated with a willingness to undergo total knee replacement (TKR) and whether this association is confounded or modified by components of socioeconomic status and health care coverage.MethodsCross‐sectional analysis was conducted among 3,530 Osteoarthritis Initiative study participants. Logistic regression models were used to assess the effect of knee pain severity (where 0 = none, 1–3 = mild, 4–7 = moderate, and 8–10 = severe) on willingness to undergo TKR. Stratified analyses were conducted to evaluate whether socioeconomic status and health care coverage modify the effect of knee pain severity on willingness.ResultsParticipants with severe knee pain, compared to participants without pain, were less willing to undergo TKR (odds ratio [OR] 0.73, 95% confidence interval [95% CI] 0.57–0.93). This association was attenuated when adjusted for age, sex, comorbidity, depression, health insurance coverage, prescription medicine coverage, health care source, education, income, employment, race, and marital status (adjusted OR 0.92, 95% CI 0.68–1.24). The odds of willingness to undergo TKR were significantly lower in those with the highest level of pain, compared to those without pain, among participants without health insurance (adjusted OR 0.08, 95% CI 0.01–0.56), but not among those with health insurance (adjusted OR 1.03, 95% CI 0.73–1.38), when adjusted for demographic, clinical, health care access, and socioeconomic factors (P = 0.015). However, <5% of participants were without health insurance.ConclusionAmong participants without health insurance, severe knee pain was paradoxically associated with less willingness to undergo TKR. Policies that improve access to quality health care may affect patient preferences and increase utilization of TKR surgery among vulnerable populations.
Enantioselective Ring Opening Reactions of Azabenzonorbornadienes with Carboxylic Acids
Authors: Zhou Yongyun , Gu Cuiping , Chen Jingchao , Zhu Meina , Yang Fan , Xu Jianbin , Fan Baomin 
Published: September 2016

AbstractThe palladium/silver (Pd/Ag) co‐catalytic system was found to be effective for the enantioselective ring opening reactions of the low reactive azabenzonorbornadienes with weak nucleophilic carboxylic acids. Both aryl and alkyl carboxylic acids are suitable nucleophiles and afforded the cis ring opening products in good yields with excellent enantioselectivities. The absolute configuration of one of the products has been confirmed by X‐ray crystal structure analysis, and a plausible reaction pathway is proposed.magnified image
Nickel‐Catalyzed Denitrated Coupling Reaction of Nitroalkenes with Aliphatic and Aromatic Alkenes
Authors: Zhang Na , Quan Zheng‐Jun , Wang Xi‐Cun 
Published: September 2016

AbstractA simple and practical denitrated coupling reaction of nitroalkenes with various alkenes using a nickel catalyst and triethoxysilane [(EtO)3SiH] as reducing agent was achieved. Under mild reaction conditions, both aliphatic and aromatic alkenes could react with nitroalkenes to obtain a series of olefins with different functional groups in satisfactory yields under an air atmosphere, which were previously difficult or impossible to access.magnified image
Overcoming the Crystallization Bottleneck: A Family of Gigantic Inorganic {Pdx}L (x=84, 72) Palladium Macrocycles Discovered using Solution Techniques
Authors: Christie Lorna G. , Surman Andrew J. , Scullion Rachel A. , Xu Feng , Long De‐Liang , Cronin Leroy 
Published: September 2016

AbstractThe {Pd84}Ac wheel, initially discovered serendipitously, is the only reported giant palladium macrocycle—a unique structure that spontaneously assembles from small building blocks. Analogues of this structure are elusive. A new modular route to {Pd84}Ac is described, allowing incorporation of other ligands, and a new screening approach to cluster discovery. Structural assignments were made of new species from solution experiments, overcoming the need for crystallographic analysis. As a result, two new palladium macrocycles were discovered: a structural analogue of the existing {Pd84}Ac wheel with glycolate ligands, {Pd84}Gly, and the next in a magic number series for this cluster family—a new {Pd72}Prop wheel decorated with propionate ligands. These findings confirm predictions of a magic number rule for the family of {Pdx} macrocycles. Furthermore, structures with variable fractions of functional ligands were obtained. Together these discoveries establish palladium clusters as a new class of tunable nanostructures. In facilitating the discovery of species that would not have been discovered by orthodox crystallization approaches, this work also demonstrates the value of solution‐based screening and characterization in cluster chemistry, as a means to decouple cluster formation, discovery, and isolation.
Aryl Radical Geometry Determines Nanographene Formation on Au(111)
Authors: Jacobse Peter H. , van den Hoogenband Adri , Moret Marc‐Etienne , Klein Gebbink Robertus J. M. , Swart Ingmar 
Published: September 2016

AbstractThe Ullmann coupling has been used extensively as a synthetic tool for the formation of C−C bonds on surfaces. Thus far, most syntheses made use of aryl bromides or aryl iodides. We investigated the applicability of an aryl chloride in the bottom‐up assembly of graphene nanoribbons. Specifically, the reactions of 10,10′‐dichloro‐9,9′‐bianthryl (DCBA) on Au(111) were studied. Using atomic resolution non‐contact AFM, the structure of various coupling products and intermediates were resolved, allowing us to reveal the important role of the geometry of the intermediate aryl radicals in the formation mechanism. For the aryl chloride, cyclodehydrogenation occurs before dehalogenation and polymerization. Due to their geometry, the planar bisanthene radicals display a different coupling behavior compared to the staggered bianthryl radicals formed when aryl bromides are used. This results in oligo‐ and polybisanthenes with predominantly fluoranthene‐type connections.
Limiting Perovskite Solar Cell Performance by Heterogeneous Carrier Extraction
Authors: Tian Wenming , Cui Rongrong , Leng Jing , Liu Junxue , Li Yajuan , Zhao Chunyi , Zhang Jun , Deng Weiqiao , Lian Tianquan , Jin Shengye 
Published: September 2016

AbstractAlthough the power conversion efficiency of perovskite solar cells has improved rapidly, a rational path for further improvement remains unclear. The effect of large morphological heterogeneity of polycrystalline perovskite films on their device performance by photoluminescence (PL) microscopy has now been studied. Contrary to the common belief on the deleterious effect of morphological heterogeneity on carrier lifetimes and diffusivities, in neat CH3NH3PbI3(Cl) polycrystalline perovskite films, the local (intra‐grain) carrier diffusivities in different grains are all surprisingly high (1.5 to 3.3 cm2 s−1; comparable to bulk single‐crystals), and the local carrier lifetimes are long (ca. 200 ns) and surprisingly homogenous among grains, and uniform across grain boundary and interior. However, there is a large heterogeneity of carrier extraction efficiency at the perovskite grain–electrode interface. Improving homogeneity at perovskite grain–electrode contacts is thus a promising direction for improving the performance of perovskite thin‐film solar cells.
Hierarchical Layer Engineering Using Supramolecular Double‐Comb Diblock Copolymers
Authors: Hofman Anton H. , Reza Mehedi , Ruokolainen Janne , ten Brinke Gerrit , Loos Katja 
Published: September 2016

AbstractThe formation of unusual multilayered parallel lamellae‐in‐lamellae in symmetric supramolecular double‐comb diblock copolymers is presented. While keeping the concentration of surfactant fixed, the number of internal layers was found to increase with molecular weight M up to 34 for the largest block copolymer. The number of internal structures n was established to scale as M0.67 and therefore enables easy design of such structures with great precision.
Water Entrapped inside Fullerene Cages: A Potential Probe for Evaluation of Bond Polarization
Authors: Hashikawa Yoshifumi , Murata Michihisa , Wakamiya Atsushi , Murata Yasujiro 
Published: September 2016

AbstractThe concept of the bond polarization is a useful tool to understand chemical reactions and fundamental properties of compounds. However, experimental considerations are limited owing to its difficulty of reliable description. We demonstrated that geometrically isolated H2O inside the cage of fullerene C60 is a possible probe to evaluate the polarization degree of covalent bonds C(C60)−X (X=heteroatom) on the C60 cage. The 1H NMR relaxation times of entrapped H2O have been systematically measured at variable temperatures for H2O@C60X (X=CR2, NR, O, and O2). The results followed in the order of electronegativities of C (2.55), N (3.04), and O (3.44), indicating that entrapped H2O can sensitively respond to the degree of the bond polarization.
Static and Dynamic Nanosheets from Selective Assembly of Geometric Macrocycle Isomers
Authors: Wang Yanqiu , Kim Yongju , Lee Myongsoo 
Published: September 2016

AbstractIn contrast to the significant advances that have been made in the construction of two‐dimensional (2D) nanostructures, the rational modification from static to dynamic 2D sheets remains a great challenge. Static and dynamic sheets formed from selective self‐assembly of geometric macrocycle isomers based on anthracene units are presented. The self‐assembly of the cis isomer generates static planar sheets, whereas the trans isomer forms dynamic rolled sheets which are reversibly unrolled upon stimulation by a thermal signal. Furthermore, the mixed solution of the two isomers exhibits self‐sorting behavior, generating the coexistence of the two independent self‐assembled structures, the planar sheets and the folded scrolls. The self‐sorted supramolecular objects with considerable shape and size differences are able to be readily separated, one isomer from the other.
A Chemoenzymatic Strategy for Imaging Cellular Phosphatidic Acid Synthesis
Authors: Bumpus Timothy W. , Baskin Jeremy M. 
Published: September 2016

AbstractPhosphatidic acid (PA) is a potent lipid secondary messenger, the synthesis of which is tightly regulated in both space and time. Established tools for detecting PA involve ex vivo analysis and do not provide information on the subcellular locations where this lipid is synthesized. Here, a chemoenzymatic strategy for imaging sites of cellular PA synthesis by phospholipase D (PLD) enzymes is reported. PLDs were found to be able to catalyze phospholipid head‐group exchange with alkynols to generate alkyne‐labeled PA analogues within cells. Subsequent fluorophore tagging through Cu‐catalyzed azide–alkyne cycloaddition enabled both visualization by fluorescence microscopy and quantification by HPLC. Our studies revealed several intracellular sites of PLD‐mediated PA synthesis. We envision applications of this approach to dissect PA‐dependent signaling pathways, image PLD activity in disease, and remodel intracellular membranes with new functionality.
Flame‐retardant mechanism of expandable polystyrene foam with a macromolecular nitrogen–phosphorus intumescent flame retardant
Authors: Wang Gang , Chen Xue , Liu Pengju , Bai Shibing 
Published: September 2016

ABSTRACTExpandable polystyrene (EPS) foam is largely used as the thermally insulating external wall in buildings and constructions, but it is extremely flammable because of the presence of almost 98% air into its porous structure, its high surface‐area‐to‐mass ratio, and its elemental composition. Lots of serious fire disasters caused by EPS foam have posed great threats to people's properties and lives in recent years. Thus, a halogen‐free, flame‐retardant EPS is urgently needed, and its preparation is still a global challenge. To solve the problem that it is easy for EPS foam to form melt dripping and difficult for it to generate a char layer during the combustion process, a macromolecular nitrogen–phosphorus intumescent flame retardant (MNP) was selected to prepare flame‐retardant EPS foam and good mechanical and flame‐retardant properties were obtained. The scanning electron microscopy characterization revealed that MNP could penetrate into the gap between the beads, and a thin physical coating layer formed on the surface of the bead. The data from the thermogravimetry–Fourier transform infrared test indicated that a nitrogenous noncombustible gas was generated by the pyrolysis of MNP. When the MNP content increased to 30%, the limiting oxygen index and the smoking density rate of the EPS–MNP foam were 28.8 and 23.6, respectively, and a UL94 V‐0 classification was achieved. In addition, the heat‐release rate, total heat‐release, smoke produce rate, and carbon dioxide production of the EPS–MNP foams all decreased obviously; this was attributed to the flame‐retardant effects of MNP in both the condensed and gas phases. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2017,134, 44356.
Autoimmune Arthritides, Rheumatoid Arthritis, Psoriatic Arthritis, or Peripheral Spondyloarthritis Following Lyme Disease
Authors: Arvikar Sheila L. , Crowley Jameson T. , Sulka Katherine B. , Steere Allen C. 
Published: September 2016

ObjectiveTo describe systemic autoimmune joint diseases that develop following Lyme disease, and to compare their clinical features with those of Lyme arthritis (LA).MethodsWe reviewed records of all adult patients referred to our LA clinic over a 13‐year period, in whom we had diagnosed a systemic autoimmune joint disease following Lyme disease. For comparison, records of patients enrolled in our LA cohort over the most recent 2‐year period were analyzed. Levels of IgG antibodies to Borrelia burgdorferi and to 3 Lyme disease–associated autoantigens were measured.ResultsWe identified 30 patients who had developed a new‐onset systemic autoimmune joint disorder a median of 4 months after Lyme disease (usually manifested by erythema migrans [EM]). Fifteen had rheumatoid arthritis (RA), 13 had psoriatic arthritis (PsA), and 2 had peripheral spondyloarthritis (SpA). The 30 patients typically had polyarthritis, and those with PsA or SpA often had previous psoriasis, axial involvement, or enthesitis. In the comparison group of 43 patients with LA, the usual clinical picture was monoarticular knee arthritis, without prior EM. Most of the patients with systemic autoimmune joint disorders were positive for B burgdorferi IgG antibodies, as detected by enzyme‐linked immunosorbent assay, but had significantly lower titers and lower frequencies of Lyme disease–associated autoantibodies than patients with LA. Prior to our evaluation, these patients had often received additional antibiotics for presumed LA, without benefit. We prescribed antiinflammatory agents, most commonly disease‐modifying antirheumatic drugs, resulting in improvement.ConclusionSystemic autoimmune joint diseases (i.e., RA, PsA, SpA) may follow Lyme disease. Development of polyarthritis after antibiotic‐treated EM, previous psoriasis, or low‐titer B burgdorferi antibodies may provide insight into the correct diagnosis.
ChemInform Abstract: Isomorphism and Solid Solutions Among Ag‐ and Au‐Selenides.
Authors: Palyanova Galina A. , Seryotkin Yurii V. , Kokh Konstantin A. , Bakakin Vladimir V. 
Published: September 2016

AbstractAg2xAuxSe (x = 0—2, in steps of 0.25) are prepared by solid state reaction of the elements (1.
ChemInform Abstract: Tuning the Mn and Fe Valence States into New Ca0.7Mn2‐xFexO4 (0 < x ≤ 0.60) Solid Solution During Reversible Redox Processes.
Authors: Lesturgez Stephanie , Goglio Graziella , Duttine Mathieu , Wattiaux Alain , Durand Etienne , Hernandez Julien , Majimel Jerome , Demourgues Alain 
Published: September 2016

AbstractCa0.7Mn2‐xFexO4 (x = 0—0.6) with Mn4+ amounts varying from 33% to 43% are prepared by an aqueous self‐combustion route involving stoichiometric mixtures of Ca, Mn, and Fe nitrates with powdered glycine in a 1:2 molar ratio (hot plate in stainless steel beaker, 220 °C) followed by firing the resultant ashes in air (850 °C, 12 h).
ChemInform Abstract: One‐Pot Synthesis of Polysubstituted Benzenes Through a N,N‐Dimethyl‐4‐aminopyridine (DMAP)‐Catalyzed [4 + 2] Benzannulation of 1,3‐Bis(sulfonyl)butadienes and γ‐Substituted Allenoates.
Authors: Chang Meijia , Wu Chengzhou , Zheng Jie , Huang You 
Published: September 2016

AbstractThe simple, metal‐free method provides the products in generally moderate yields.
ChemInform Abstract: Direct Synthesis of Nitriles from Cleavage of C=C Double Bond with Nitrite as the Nitrogen Source and Oxidant.
Authors: Liu Qiang , Fang Bao , Bai Xiaohui , Liu Yuan , Wu Yao , Xu Guiming , Guo Cancheng 
Published: September 2016

AbstractA variety of styrenes undergo nitrogenation reaction to afford the corresponding nitriles in high yields, whereas the reaction of internal alkenes (III) and (IV) proceeds sluggishly even under the optimized conditions.
ChemInform Abstract: Diastereo‐ and Enantioselective Synthesis of Spiro‐Pyrrolidine‐Pyrazolones by Squaramide‐Catalyzed Cascade Aza‐Michael/Michael Reactions.
Authors: Li Jun‐Hua , Wen Hongliang , Liu Lei , Du Da‐Ming 
Published: September 2016

AbstractA series of novel spiropyrrolidine‐pyrazolones having three contiguous stereocenters are synthesized by cyclocondensation of arylidene pyrazolones (I) with tosylaminomethyl enones (II) in the presence of a squaramide catalyst.
ChemInform Abstract: Visible‐Light Photoredox Synthesis of Internal Alkynes Containing Quaternary Carbons.
Authors: Gao Chang , Li Jingjing , Yu Jipan , Yang Haijun , Fu Hua 
Published: September 2016

Abstractvia coupling reactions of N‐phthalimidoyl oxalates of tert‐alcohols with arylsulfonylalkynes (II)
ChemInform Abstract: Uniting C1‐Ammonium Enolates and Transition Metal Electrophiles via Cooperative Catalysis: The Direct Asymmetric α‐Allylation of Aryl Acetic Acid Esters.
Authors: Schwarz Kevin J. , Amos Jessica L. , Klein J. Cullen , Do Dung T. , Snaddon Thomas N. 
Published: September 2016

AbstractAllylmethane sulfonate as well as diverse aryl substituted allyl carbonates efficiently react with pentafluorophenyl 2‐arylacetates to form α‐allylated products in high yields and with very high enantiomeric excesses.
ChemInform Abstract: Catalytic Enantioselective Conversion of Epoxides to Thiiranes.
Authors: Liao Saihu , Leutzsch Markus , Monaco Mattia Riccardo , List Benjamin 
Published: September 2016

AbstractThe Broensted acid‐catalyzed kinetic resolution of variously functionalized aryl epoxides delivers the thiiranes as well as the epoxides in very high yields and with very high enantiomeric excesses.
ChemInform Abstract: Copper‐Mediated Effective Synthesis of S‐Trifluoromethyl Esters by Trifluoromethylthiolation of Acid Chlorides.
Authors: Zhang Mengjia , Chen Jinliang , Chen Zhirong , Weng Zhiqiang 
Published: September 2016

AbstractThe reaction of copper bipyridine complex (I) with acyl chlorides (II) and (IV) leads to desired S‐trifluoromethyl esters (III) and (V) in good to excellent yields.
ChemInform Abstract: Lewis Acid‐Catalyzed Tandem Synthesis of 9‐Sulfonylamino‐ and 9‐Arylfluorenes.
Authors: Huang Dayun , Yang Weiguang , Zhang Jianlan , Wang Xuesong , Wang Xinyan , Hu Yuefei 
Published: September 2016

Abstract9‐Arylfluorenes are simply prepared by heating a mixture of 2‐formyl biphenyls, Tos‐NCO, and arenes.
ChemInform Abstract: Phosphine‐Mediated Highly Enantioselective Spirocyclization with Ketimines as Substrates.
Authors: Han Xiaoyu , Chan Wai‐Lun , Yao Weijun , Wang Yongjiang , Lu Yixin 
Published: September 2016

AbstractIsatin derived ketimines are applied for the first time in highly enantioselective phosphine‐catalyzed [3 + 2] annulation reactions with allenes.
ChemInform Abstract: Synthesis under Moderate Pressure of 3‐Imidazo[1,2‐a]pyridinylidene Pyrrol‐2‐ones.
Authors: Masurier Nicolas , Lebrun Aurelien , Canitrot Damien , Chezal Jean‐Michel , Moreau Emmanuel 
Published: September 2016

AbstractFuran‐2‐ones (I) are converted into their pyrrol‐2‐one analogues upon treatment with aqueous ammonia under moderate pressure.
ChemInform Abstract: A Versatile Access to Vicinal Diamine Motifs by Highly anti‐Selective Asymmetric Vinylogous Mannich Reactions: An Efficient Total Synthesis of (+)‐Absouline.
Authors: Ye Jian‐Liang , Chen Hang , Zhang Yu‐Feng , Huang Pei‐Qiang 
Published: September 2016

AbstractThe vicinal diamine motif (Vd) is utilized in the efficient total synthesis of (+)‐absouline (VI).
ChemInform Abstract: Friedel—Crafts Fluoroacetylation of Indoles with Fluorinated Acetic Acids for the Synthesis of Fluoromethyl Indol‐3‐yl Ketones under Catalyst‐ and Additive‐Free Conditions.
Authors: Yao Shun‐Jiang , Ren Zhi‐Hui , Wang Yao‐Yu , Guan Zheng‐Hui 
Published: September 2016

AbstractVarious indole substrates such as (I), (VI), (IX) are used for the introduction of fluorinated acyl side chains at position 3.
ChemInform Abstract: Broensted Acid Catalyzed [3 + 2]‐Cycloaddition of 2‐Vinylindoles with in situ Generated 2‐Methide‐2H‐indoles: Highly Enantioselective Synthesis of Pyrrolo[1,2‐a]indoles.
Authors: Bera Kalisankar , Schneider Christoph 
Published: September 2016

AbstractThe title systems, important structural elements in natural products and pharmaceutical agents, are readily available in a highly enantioselective manner in the presence of the chiral phosphoric acid BPA.