bluuebunny/crossref_metadata_2025_split huggingface dataset:
Cascade Reactions: A Multicomponent Approach to Functionalized Indane Derivatives by a Tandem Palladium‐ Catalyzed Carbamoylation/Carbocylization Process
Authors: Gabriele Bartolo , Veltri Lucia , Mancuso Raffaella , Carfagna Carla 
Published: July 2014

AbstractA novel, multicomponent and stereoselective approach to functionalized indane derivatives is reported. It is based on a tandem process consisting of Pd‐catalyzed oxidative carbamoylation of 2‐(2‐ethynylbenzyl)malonates with carbon monoxide, a secondary amine, and oxygen (with formation of a propiolamide intermediate), followed by carbocyclization, occurring through intramolecular addition of an in situ formed carbanion to the propiolamide moiety.magnified image
Ferrocenyl‐Based P,N Catalysts for the Mono‐α‐Arylation of Acetone
Authors: Gäbler Christian , Korb Marcus , Schaarschmidt Dieter , Hildebrandt Alexander , Lang Heinrich 
Published: July 2014

AbstractThe novel air‐stable diferrocenyl‐based P,N ligands PFc2(C6H4‐2‐NMe2) (1) and PFc2(C6H4‐2‐piperidyl) (2) [Fc=Fe(η5‐C5H4)(η5‐C5H5)] for the highly effective palladium‐catalyzed mono‐α‐arylation of acetone are reported. High yields could be obtained for the CC coupling of several chloro‐ and bromoarenes at palladium loadings as low as 0.5 mol% of [Pd(cinnamyl)Cl]2.magnified image
Conversion of Thebaine to Oripavine and Other Useful Intermediates for the Semisynthesis of Opiate‐Derived Agents: Synthesis of Hydromorphone
Authors: Murphy Brennan , Šnajdr Ivan , Machara Aleš , Endoma‐Arias Mary Ann A. , Stamatatos Theocharis C. , Cox D. Phillip , Hudlický Tomáš 
Published: July 2014

AbstractThebaine was converted to oripavine in three steps by employing two different modes of protection of the diene moiety; as an iron tricarbonyl complex and as a Diels–Alder adduct with thioformyl cyanide. The two C‐ring‐protected thebaine derivatives were subjected to 3‐O‐demethylation by four different protocols, providing oripavine derivatives, which yielded oripavine after deprotection. Oripavine was then converted to hydromorphone by a three‐step process of ketalization, hydrogenation, and deprotection, without the isolation of intermediates.magnified image
NMR Signatures of the Active Sites in Sn‐β Zeolite
Authors: Wolf Patrick , Valla Maxence , Rossini Aaron J. , Comas‐Vives Aleix , Núñez‐Zarur Francisco , Malaman Bernard , Lesage Anne , Emsley Lyndon , Copéret Christophe , Hermans Ive 
Published: July 2014

AbstractDynamic nuclear polarization surface enhanced NMR (DNP‐SENS), Mössbauer spectroscopy, and computational chemistry were combined to obtain structural information on the active‐site speciation in Sn‐β zeolite. This approach unambiguously shows the presence of framework SnIV‐active sites in an octahedral environment, which probably correspond to so‐called open and closed sites, respectively (namely, tin bound to three or four siloxy groups of the zeolite framework).
Molecular Salt Effects in the Gas Phase: Tuning the Kinetic Basicity of [HCCLiCl]− and [HCCMgCl2]− by LiCl and MgCl2
Authors: Khairallah George N. , da Silva Gabriel , O'Hair Richard A. J. 
Published: July 2014

AbstractA combination of gas‐phase ion–molecule reaction experiments and theoretical kinetic modeling is used to examine how a salt can influence the kinetic basicity of organometallates reacting with water. [HCCLiCl]− reacts with water more rapidly than [HCCMgCl2]−, consistent with the higher reactivity of organolithium versus organomagnesium reagents. Addition of LiCl to [HCCLiCl]− or [HCCMgCl2]− enhances their reactivity towards water by a factor of about 2, while addition of MgCl2 to [HCCMgCl2]− enhances its reactivity by a factor of about 4. Ab initio calculations coupled with master equation/RRKM theory kinetic modeling show that these reactions proceed via a mechanism involving formation of a water adduct followed by rearrangement, proton transfer, and acetylene elimination as either discrete or concerted steps. Both the energy and entropy requirements for these elementary steps need to be considered in order to explain the observed kinetics.
Tuning Lanthanide Reactivity Towards Small Molecules with Electron‐Rich Siloxide Ligands
Authors: Andrez Julie , Pécaut Jacques , Bayle Pierre‐Alain , Mazzanti Marinella 
Published: July 2014

AbstractThe synthesis, structure, and reactivity of stable homoleptic heterometallic LnL4K2 complexes of divalent lanthanide ions with electron‐rich tris(tert‐butoxy)siloxide ligands are reported. The [Ln(OSi(OtBu)3)4K2] complexes (Ln=Eu, Yb) are stable at room temperature, but they promote the reduction of azobenzene to yield the KPhNNPh radical anion as well as the reductive cleavage of CS2 to yield CS32− as the major product. The EuIII complex of the radical anion PhNNPh is structurally characterized. Moreover, [Yb(OSi(OtBu)3)4K2] can reduce CO2 at room temperature. Release of the reduction products in D2O shows the quantitative formation of both oxalate and carbonate in a 1:2.2 ratio. The bulky siloxide ligands enforce the labile binding of the reduction products providing the opportunity to establish a closed synthetic cycle for the YbII‐mediated CO2 reduction. These studies show that the presence of four electron‐rich siloxide ligands renders their EuII and YbII complexes highly reactive.
Adsorption von I2 durch makrocyclische Polyaza‐Dithiophenolato‐Komplexe unter Bildung von Charge‐Transfer‐Addukten
Authors: Golecki Matthias , Beyer Norman , Steinfeld Gunther , Lozan Vasile , Voitekhovich Sergei , Sehabi Muhamed , Möllmer Jens , Krüger Hans‐Jörg , Kersting Berthold 
Published: July 2014

AbstractDer makrocyclische Komplex [Ni2(L)(OAc)]ClO4 kann Iod bis zu 270 % seines Eigengewichts gemäß einer Masse von 17 I2‐Molekülen adsorbieren, obwohl seine Struktur keinerlei permanente Porosität aufweist. Schwingungsspektroskopische und kristallographische Untersuchungen zeigen, dass zunächst zwei I2‐Moleküle in Form von Thiophenolat→I2‐CT‐Addukten gebunden werden, welche die weitere Diffusion und sukzessive Sorption anderer I2‐Moleküle zu einem Polyiodid‐artigen Netzwerk ermöglichen. Die effizienten Sorptions‐ und Desorptionseigenschaften machen dieses Material geeignet für den Nachweis, die Speicherung oder die kontrollierte Abgabe von Iod.
Two‐Electron Reductive Carbonylation of Terminal Uranium(V) and Uranium(VI) Nitrides to Cyanate by Carbon Monoxide
Authors: Cleaves Peter A. , King David M. , Kefalidis Christos E. , Maron Laurent , Tuna Floriana , McInnes Eric J. L. , McMaster Jonathan , Lewis William , Blake Alexander J. , Liddle Stephen T. 
Published: July 2014

AbstractTwo‐electron reductive carbonylation of the uranium(VI) nitride [U(TrenTIPS)(N)] (2, TrenTIPS=N(CH2CH2NSiiPr3)3) with CO gave the uranium(IV) cyanate [U(TrenTIPS)(NCO)] (3). KC8 reduction of 3 resulted in cyanate dissociation to give [U(TrenTIPS)] (4) and KNCO, or cyanate retention in [U(TrenTIPS)(NCO)][K(B15C5)2] (5, B15C5=benzo‐15‐crown‐5 ether) with B15C5. Complexes 5 and 4 and KNCO were also prepared from CO and the uranium(V) nitride [{U(TrenTIPS)(N)K}2] (6), with or without B15C5, respectively. Complex 5 can be prepared directly from CO and [U(TrenTIPS)(N)][K(B15C5)2] (7). Notably, 7 reacts with CO much faster than 2. This unprecedented f‐block reactivity was modeled theoretically, revealing nucleophilic attack of the π* orbital of CO by the nitride with activation energy barriers of 24.7 and 11.3 kcal mol−1 for uranium(VI) and uranium(V), respectively. A remarkably simple two‐step, two‐electron cycle for the conversion of azide to nitride to cyanate using 4, NaN3 and CO is presented.
[FeFe] Hydrogenase: Protonation of {2Fe3S} Systems and Formation of Super‐reduced Hydride States
Authors: Jablonskytė Aušra , Wright Joseph A. , Fairhurst Shirley A. , Webster Lee R. , Pickett Christopher J. 
Published: July 2014

AbstractThe synthesis and crystallographic characterization of a complex possessing a well‐defined {2Fe3S(μ‐H)} core gives access to a paramagnetic bridging hydride with retention of the core geometry. Chemistry of this 35‐electron species within the confines of a thin‐layer FTIR spectro‐electrochemistry cell provides evidence for a unprecedented super‐reduced FeI(μ‐H)FeI intermediate.
Induction of Interleukin‐6 Production by Rituximab in Human B Cells
Authors: Jones Jonathan D. , Hamilton B. JoNell , Skopelja Sladjana , Rigby William F. C. 
Published: July 2014

ObjectiveRituximab (RTX), an anti‐CD20 monoclonal antibody, is highly effective in the treatment of several autoimmune diseases. The mechanism by which RTX treatment improves rheumatoid arthritis and antineutrophil cytoplasmic antibody–associated vasculitis is not easily related to B cell depletion alone. Prior studies have shown that RTX mediates a rapid stripping of CD20 and CD19 from the human B cell through a process known as trogocytosis. The aim of the present study was to investigate whether changes in B cell phenotype resulting from trogocytosis would diminish the ability of B cells to promote autoimmune disease.MethodsHuman peripheral blood mononuclear cells were cultured with RTX under conditions that permitted trogocytosis. Changes in B cell phenotype and cytokine production were measured in the basal state and under conditions of activation with interleukin‐4 (IL‐4)/anti‐CD40. The effects of RTX were characterized in terms of a requirement for interaction with the Fcγ receptor (FcγR) and other Fc‐dependent interactions.ResultsTrogocytosis induced a marked loss of surface CD19, IgD, CD40, and B cell–activating factor receptor, but did not alter induction of CD86 expression on purified B cells following IL‐4/anti‐CD40 treatment. Unexpectedly, RTX‐dependent trogocytosis of normal human B cells in vitro led to a rapid up‐regulation of IL‐6 production, with no effect on the production of tumor necrosis factor α, IL‐1β, interferon‐γ, or IL‐10. This effect was Fc‐dependent and required the presence of an FcγR‐bearing cell. Moreover, this effect involved the release of preformed intracellular IL‐6 protein, as well as marked increases in IL‐6 messenger RNA levels.ConclusionRTX‐mediated trogocytosis of B cells in vitro results in acute production and release of IL‐6. The nature of this effect and how it is related to the acute infusion reactions seen with RTX administration remain to be determined.
Clinical Features, Treatment, and Outcome of Macrophage Activation Syndrome Complicating Systemic Juvenile Idiopathic Arthritis: A Multinational, Multicenter Study of 362 Patients
Authors: Minoia Francesca , Davì Sergio , Horne AnnaCarin , Demirkaya Erkan , Bovis Francesca , Li Caifeng , Lehmberg Kai , Weitzman Sheila , Insalaco Antonella , Wouters Carine , Shenoi Susan , Espada Graciela , Ozen Seza , Anton Jordi , Khubchandani Raju , Russo Ricardo , Pal Priyankar , Kasapcopur Ozgur , Miettunen Paivi , Maritsi Despoina , Merino Rosa , Shakoory Bita , Alessio Maria , Chasnyk Vyacheslav , Sanner Helga , Gao Yi‐Jin , Huasong Zeng , Kitoh Toshiyuki , Avcin Tadej , Fischbach Michel , Frosch Michael , Grom Alexei , Huber Adam , Jelusic Marija , Sawhney Sujata , Uziel Yosef , Ruperto Nicolino , Martini Alberto , Cron Randy Q. , Ravelli Angelo ,   on behalf of the Pediatric Rheumatology International Trials Organization, the Childhood Arthritis and Rheumatology Research Alliance, the Pediatric Rheumatology Collaborative Study Group, and the Histiocyte Society
Published: July 2014

ObjectiveTo describe the clinical, laboratory, and histopathologic features, current treatment, and outcome of patients with macrophage activation syndrome (MAS) complicating systemic juvenile idiopathic arthritis (JIA).MethodsIn this multinational, multicenter study, pediatric rheumatologists and hemato‐oncologists entered patient data collected retrospectively into a web‐based database.ResultsA total of 362 patients, 22% of whom had MAS at the onset of systemic JIA, were included in the study by 95 investigators from 33 countries. The most frequent clinical manifestations were fever (96%), hepatomegaly (70%), and splenomegaly (58%). Central nervous system dysfunction and hemorrhages were recorded in 35% and 20% of the patients, respectively. Platelet count and liver transaminase, ferritin, lactate dehydrogenase, triglyceride, and d‐dimer levels were the sole laboratory biomarkers showing a percentage change of >50% between the pre‐MAS visit and MAS onset. Evidence of macrophage hemophagocytosis was found in 60% of the patients who underwent bone marrow aspiration. MAS occurred most frequently in the setting of active underlying disease, in the absence of a specific trigger. Nearly all patients were given corticosteroids, and 61% received cyclosporine. Biologic medications and etoposide were given to 15% and 12% of the patients, respectively. Approximately one‐third of the patients required admission to the intensive care unit (ICU), and the mortality rate was 8%.ConclusionThis study provides information on the clinical spectrum and current management of systemic JIA–associated MAS through the analysis of a very large patient sample. MAS remains a serious condition, as a sizeable proportion of patients required admission to the ICU or died.
Robust H∞ Output Tracking Control with Partly Quantized Information
Authors: Ge Yang , Wang Jingcheng , Zhang Langwen , Li Chuang 
Published: July 2014

AbstractThis paper is concerned with the stability and output tracking problems of networked control systems (NCSs) with partly quantized information. Both the remote and local systems are considered. The state variables transported from the remote system experiences time delays and quantization errors, while the local state variables do not. The purpose is to design a state feedback controller which guarantees that the output of the local system tracks the output of the remote system in the H∞ sense. This consideration is widely appeared in remote assistant systems. Based on the Lyapunov–Krasovskii (L‐K) functional approach, sufficient conditions on the existence of a quantized robust H∞ output tracking controller for NCSs are presented in terms of bilinear matrix inequalities (BMIs). Furthermore, a cone complementarity algorithm is used to convert these BMIs into a convex optimization problem. Finally, a simulation example is given to demonstrate the efficiency of the proposed method.
Identification and Compensation of Force Ripple in PMSLM using a JITL Technique
Authors: Lu Shaowu , Tang Xiaoqi , Song Bao , Zheng Shiqi , Zhou FengXing 
Published: July 2014

AbstractThis paper presents an adaptive compensation scheme for reducing the force ripple effects in permanent magnet synchronous linear motor (PMSLM). Firstly, when the velocity of a linear motor is close to zero, based on a fast Fourier transform (FFT) analysis, the dominant displacement periodicity of the force ripple can be obtained for simplifying the ripple model. Next, to enhance the identification accuracy and guarantee the real‐time performance of the linear servo system simultaneously, an improved just‐in‐time learning (JITL) algorithm is proposed to estimate the ripple model parameters. Finally, based on the identification results, an adaptive feedforward controller is implemented in the linear servo system to compensate the force ripple. The main motivation of this paper is the extension of the identification methods to improve the servo control performance in industrial applications. Simulation and experimental results demonstrate the effectiveness of the proposed method, even when compared to a traditional compensation method based on a recursive least squares algorithm.
Pregnancy outcome in women assigned an ICD‐9/ICD‐9‐CM 655.0 code “central nervous system malformation in fetus affecting management of pregnancy”: Can these codes aid in surveillance for central nervous system defects?
Authors: Evans Jane A 
Published: July 2014

BackgroundThe difficulty many birth defects registries have in identifying early pregnancy terminations can lead to significant underreporting of certain types of malformations. This study was designed to determine the potential benefit of using maternal ICD‐9 codes relating to management of pregnancy due to fetal anomaly in surveillance of central nervous system (CNS) defects (655.0).MethodsWomen assigned the ICD‐9/ICD‐9‐CM (henceforth termed ICD‐9) code 655.0 between 1990 and 2000 were ascertained from two administrative health databases in Manitoba, Canada, one relating to maternal serum screening and one based on hospital discharges. Information was collected on the type of CNS defect identified and whether it was isolated or associated with other anomalies. The relationship of these variables to pregnancy outcome and its potential impact on surveillance for these types of defects was explored.ResultsNeural tube defects were the most common finding (67%) identified in the fetuses/infants of women assigned code 655.0, followed by hydrocephaly (20%) and Dandy‐Walker anomaly (6%), but the proportion of neural tube defect cases declined after food fortification with folic acid. Termination of pregnancy occurred in ∼50% of neural tube defect cases, 18% before 20 weeks of gestation, but was rare for other CNS defects.ConclusionThe maternal ICD‐9 code 655.0 had a very high (97%) positive predictive value for identifying fetuses with a CNS defect; 655.00 was particularly effective in identifying neural tube defects pregnancies terminated before 20 weeks gestation that would be difficult to ascertain, especially by passive surveillance systems using infant related data alone. Birth Defects Research (Part A) 100:848–851, 2014. © 2014 Wiley Periodicals, Inc.
Hydranencephaly in a newborn with a FLVCR2 mutation and prenatal exposure to cocaine
Authors: Soster Erica L. , Tucker Megan , Escobar Luis F. , Vance Gail H. 
Published: July 2014

BackgroundHydranencephaly is a relatively rare but severe structural brain abnormality that often results in perinatal death. Although several factors including infection and multiple births have been reported to be associated with this birth defect, the underlying etiology is not well understood. Recently, FLVCR2 gene mutations have been implicated in a subset of hydranencephaly cases, following an autosomal recessive pattern of inheritance.CaseWe report a male infant with hydranencephaly found to have a previously unreported six amino acid deletion in one copy of the FLVCR2 gene following a pregnancy complicated by poor prenatal care and maternal cocaine use. Although our patient currently presents with developmental delays, he is showing progress and gaining some skills.ConclusionWe discuss the possibility of a synergistic effect between the FLVCR2 genetic mutation and environmental cocaine exposure, creating a susceptible brain, as an explanation for this infant's phenotype. This case demonstrates the potential clinical utility of testing for mutations in FLVCR2 for patients with hydranencephaly after other possible etiologies, such as congenital infection, have been reasonably eliminated. Current literature on FLVCR2 is relatively sparse; identifying additional patients with similar mutations will aid in defining the clinical significance of a gene mutation and the contribution to the etiology of hydranencephaly. Birth Defects Research (Part A) 103:45–50, 2015. © 2014 Wiley Periodicals, Inc.
Svelte integrated delivery system performance examined through diagnostic catheter delivery: The SPEED registry
Authors: Khattab Ahmed A. , Nijhoff Freek , Schofer Joachim , Berland Jacques , Meier Bernhard , Nietlispach Fabian , Agostoni Pierfrancesco , Brucks Steffen , Stella Pieter 
Published: July 2014

AimsThe multi‐center SPEED registry evaluated the procedural success and in‐hospital clinical outcomes of direct stenting with the Svelte ‘all‐in‐one’ coronary stent Integrated Delivery System (IDS) through diagnostic catheters to identify the clinical indications for which this approach is appropriately suited.Methods & resultsForty‐eight (48) patients with 54 lesions of lengths ≤20 mm and RVD 2.5–3.5 mm were targeted for direct stenting through diagnostic catheters (4–6F) via radial or femoral approach. Procedural characteristics early in an investigator's experience (28 lesions) were compared with outcomes following experience (26 lesions). Procedure, device and strategy success were realized in 54 (100%), 50 (93%) and 46 (85%) lesions, respectively, with strategy success significantly related to RVD (P = 0.05), lesion location (P = 0.01), and diagnostic catheter size (P = 0.05). Significant improvement in crossing and intervention time and trends toward improvement in device and strategy success, reductions in procedure and radiation time and contrast use were observed.ConclusionsDirect stenting through diagnostic catheters via radial or femoral approach using the Svelte IDS is feasible and associated with good in‐hospital outcomes. This approach offers the attractive option of assessing lesions via diagnostic catheter and, depending upon vessel anatomy and lesion morphology, continuing with ad‐hoc interventional treatment using the same diagnostic catheter. Improvements in strategy success and procedural efficiencies, based on operator experience, facilitate catheter downsizing and reduce intervention time, ancillary product use and overall procedure costs. © 2014 Wiley Periodicals, Inc.
Copper in Photocatalysis
Authors: Paria Suva , Reiser Oliver 
Published: July 2014

AbstractLight‐induced electron transfer (CuI to CuII), oxidative addition (CuI to CuIII), or the activation of copper alkene or alkyne complexes are possible key steps that offer unique possibilities for organic synthesis, including [2+2]‐cycloadditions, cross‐coupling reactions or atom transfer radical additions. This Minireview provides an overview on the photophysical properties of photocatalysts based on copper and on synthetic transformations mediated by them.
Bubble Volume and Aspect Ratio Generated in Non‐Newtonian Fluids
Authors: Fan Wenyuan , Sun Yawei , Chen Hui 
Published: July 2014

AbstractBubble formation from an orifice submerged in quiescent polyacrylamide aqueous solution was investigated numerically with a sharp‐interface coupled level‐set/volume‐of‐fluid method based on the rheological characteristics of the fluid. In both non‐Newtonian fluids and Newtonian fluids, the numerical approach was able to capture accurately the deformation of the bubble surface, validated by comparison with experimental results. The effects of orifice diameter, solution mass concentration, and gas flow rate on bubble volume and aspect ratio were evaluated. Both the instantaneous and detached volume decrease with the orifice diameter but increase with mass concentration and gas flow rate. The aspect ratio at the departing point tends to rise with the orifice diameter and mass concentration and falls with the gas flow rate.
High Resolution Scanning Tunneling Microscopy of a 1D Coordination Polymer with Imidazole‐Based N,N,O Ligands on HOPG
Authors: Fischer Nina V. , Mitra Utpal , Warnick Karl‐Georg , Dremov Viacheslav , Stocker Michael , Wölfle Thorsten , Hieringer Wolfgang , Heinemann Frank W. , Burzlaff Nicolai , Görling Andreas , Müller Paul 
Published: July 2014

AbstractNovel κ3‐N,N,O ligands tend to form 1D coordination polymer strands. Deposition of 1D structures on highly oriented pyrolytic graphite (HOPG) was achieved from diluted solutions and polymer strands have been studied on HOPG by AFM/STM. Single strands were mapped by STM and their electronic properties were subsequently characterized by current imaging tunneling spectroscopy (CITS). Periodic density functional calculations simulating a polymer strand deposited on a HOPG surface are in agreement with the zig‐zag structure indicated by experimental findings. Both the observed periodicity and the Zn–Zn distances can be reproduced in the simulations. Van der Waals interactions were found to play a major role for the geometry of the isolated polymer strand, for the adsorption geometry on HOPG, as well as for the adsorption energy.