bluuebunny/crossref_metadata_2025_split huggingface dataset:
Fast bias‐constrained optimal FIR filtering for time‐invariant state space models
Authors: Zhao Shunyi , Shmaliy Yuriy S. , Ji Guoli , Khan Sanowar H. 
Published: December 2016

SummaryThis paper combines the finite impulse response filtering with the Kalman structure (predictor/corrector) and proposes a fast iterative bias‐constrained optimal finite impulse response filtering algorithm for linear discrete time‐invariant models. In order to provide filtering without any requirement of the initial state, the property of unbiasedness is employed. We first derive the optimal finite impulse response filter constrained by unbiasedness in the batch form and then find its fast iterative form for finite‐horizon and full‐horizon computations. The corresponding mean square error is also given in the batch and iterative forms. Extensive simulations are provided to investigate the trade‐off with the Kalman filter. We show that the proposed algorithm has much higher immunity against errors in the noise covariances and better robustness against temporary model uncertainties. The full‐horizon filter operates almost as fast as the Kalman filter, and its estimate converges with time to the Kalman estimate. Copyright © 2016 John Wiley & Sons, Ltd.
Substrate‐Regiocontrolled Synthesis of Enantioenriched Allylic Amines by Palladium‐Catalysed Asymmetric Allylic Amination: Formal Synthesis of Fagomine
Authors: Soriano Sébastien , Escudero‐Casao Margarita , Matheu M. Isabel , Díaz Yolanda , Castillón Sergio 
Published: December 2016

AbstractBranched allyl amines or linear amines can be obtained from E‐4‐hydroxybuten‐2‐yl methyl carbonate using the palladium/1,2‐diaminocyclohexane (DACH)‐catalysed allylic amination by just starting from the unprotected or the protected derivative, respectively. Unhindered primary amines can be used as nucleophiles, thus enlarging the scope of the Pd/DACH catalytic system. Hydrogen bonding involving the free hydroxy group in the unprotected allylic carbonate is proposed to be responsible for the control of the regioselectivity to afford branched isomers, obtained in high ee. A short and enantioselective formal synthesis of the glycosidase inhibitor fagomine is described using this method.magnified image
Interacting spinning fermions with quasi‐random disorder
Authors: Mastropietro Vieri 
Published: December 2016

Interacting spinning fermions with strong quasi‐random disorder are analyzed via rigorous Renormalization Group (RG) methods combined with KAM techniques. The correlations are written in terms of an expansion whose convergence follows from number‐theoretical properties of the frequency and cancellations due to Pauli principle. A striking difference appears between spinless and spinning fermions; in the first case there are no relevant effective interactions while in presence of spin an additional relevant quartic term is present in the RG flow. The large distance exponential decay of the correlations present in the non interacting case, consequence of the single particle localization, is shown to persist in the spinning case only for temperatures greater than a power of the many body interaction, while in the spinless case this happens up to zero temperature.
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Continuous Flow Synthesis and Purification of Aryldiazomethanes through Hydrazone Fragmentation
Authors: Lévesque Éric , Laporte Simon T. , Charette André B. 
Published: December 2016

AbstractElectron‐rich diazo compounds, such as aryldiazomethanes, are powerful reagents for the synthesis of complex structures, but the risks associated with their toxicity and instability often limit their use. Flow chemistry techniques make these issues avoidable, as the hazardous intermediate can be used as it is produced, avoiding accumulation and handling. Unfortunately, the produced stream is often contaminated with other reagents and by‐products, making it incompatible with many applications, especially in catalysis. Herein is reported a metal‐free continuous flow method for the production of aryldiazomethane solutions in a non‐coordinating solvent from easily prepared, bench‐stable sulfonylhydrazones. All by‐products are removed by an in‐line aqueous wash, leaving a clean, base‐free diazo stream. Three successful sensitive metal‐catalyzed transformations demonstrated the value of the method.
Highly Site Selective Formal [5+2] and [4+2] Annulations of Isoxazoles with Heterosubstituted Alkynes by Platinum Catalysis: Rapid Access to Functionalized 1,3‐Oxazepines and 2,5‐Dihydropyridines
Authors: Shen Wen‐Bo , Xiao Xin‐Yu , Sun Qing , Zhou Bo , Zhu Xin‐Qi , Yan Juan‐Zhu , Lu Xin , Ye Long‐Wu 
Published: December 2016

AbstractPlatinum‐catalyzed formal [5+2] and [4+2] annulations of isoxazoles with heterosubstituted alkynes enabled the atom‐economical synthesis of valuable 1,3‐oxazepines and 2,5‐dihydropyridines, respectively. Importantly, this Pt catalysis not only led to unique reactivity dramatically divergent from that observed under Au catalysis, but also proceeded via unprecedented α‐imino platinum carbene intermediates.
Glucose‐Responsive Sequential Generation of Hydrogen Peroxide and Nitric Oxide for Synergistic Cancer Starving‐Like/Gas Therapy
Authors: Fan Wenpei , Lu Nan , Huang Peng , Liu Yi , Yang Zhen , Wang Sheng , Yu Guocan , Liu Yijing , Hu Junkai , He Qianjun , Qu Junle , Wang Tianfu , Chen Xiaoyuan 
Published: December 2016

AbstractGlucose is a key energy supplier and nutrient for tumor growth. Herein, inspired by the glucose oxidase (GOx)‐assisted conversion of glucose into gluconic acid and toxic H2O2, a novel treatment paradigm of starving‐like therapy is developed for significant tumor‐killing effects, more effective than conventional starving therapy by only cutting off the energy supply. Furthermore, the generated acidic H2O2 can oxidize l‐Arginine (l‐Arg) into NO for enhanced gas therapy. By using hollow mesoporous organosilica nanoparticle (HMON) as a biocompatible/biodegradable nanocarrier for the co‐delivery of GOx and l‐Arg, a novel glucose‐responsive nanomedicine (l‐Arg‐HMON‐GOx) has been for the first time constructed for synergistic cancer starving‐like/gas therapy without the need of external excitation, which yields a remarkable H2O2–NO cooperative anticancer effect with minimal adverse effect.
Synthesis of Functionalized [3], [4], [5] and [6]Dendralenes through Palladium‐Catalyzed Cross‐Couplings of Substituted Allenoates
Authors: Lippincott Daniel J. , Linstadt Roscoe T. H. , Maser Michael R. , Lipshutz Bruce H. 
Published: December 2016

AbstractA mild method for the synthesis of highly functionalized [3]–[6]dendralenes is reported, representing a general strategy to diversely substituted higher homologues of the dendralenes. The methodology utilizes allenoates bearing various substitution patterns, along with a wide range of boron and alkenyl nucleophiles that couple under palladium catalysis leading to sp‐, sp2‐, and sp3‐substituted arrays. Regioselective transformations of the newly formed unsymmetrical dendralene derivatives are demonstrated. The use of micellar catalysis, where water is the global reaction medium, and room temperature reaction conditions, highlights the green nature of this technology.
Single Fusion Events at Polarized Liquid–Liquid Interfaces
Authors: Laborda Eduardo , Molina Angela , Espín Vanesa Fernández , Martínez‐Ortiz Francisco , García de la Torre José , Compton Richard G. 
Published: December 2016

AbstractA new electrochemical framework for tracking individual soft particles in solution and monitoring their fusion with polarized liquid–liquid interfaces is reported. The physicochemical principle lies in the interfacial transfer of an ionic probe confined in the particles dispersed in solution and that is released upon their collision and fusion with the fluid interface. As a proof‐of‐concept, spike‐like transients of a stochastic nature are reported in the current–time response of 1,2‐dichloroethane(DCE)|water(W) submilli‐interfaces after injection of DCE‐in‐W emulsions. The sign and potential dependence of the spikes reflect the charge and lipophilicity of the ionic load of the droplets. A comparison with dynamic light scattering measurements indicates that each spike is associated with the collision of a single sub‐picoliter droplet. This opens a new framework for the study of single fusion events at the micro‐ and nanoscale and of ion transport across biomimetic soft interfaces.
Knight Shift in 13C NMR Resonances Confirms the Coordination of N‐Heterocyclic Carbene Ligands to Water‐Soluble Palladium Nanoparticles
Authors: Asensio Juan M. , Tricard Simon , Coppel Yannick , Andrés Román , Chaudret Bruno , de Jesús Ernesto 
Published: December 2016

AbstractThe coordination of N‐heterocyclic carbene (NHC) ligands to the surface of 3.7 nm palladium nanoparticles (PdNPs) can be unambiguously established by observation of Knight shift (KS) in the 13C resonance of the carbenic carbon. In order to validate this coordination, PdNPs with sizes ranging from 1.3 to 4.8 nm were prepared by thermal decomposition or reduction with CO of a dimethyl NHC PdII complex. NMR studies after 13CO adsorption established that the KS shifts the 13C resonances of the chemisorbed molecules several hundreds of ppm to high frequencies only when the particle exceeds a critical size of around 2 nm. Finally, the resonance of a carbenic carbon is reported to be Knight‐shifted to 600 ppm for 13C‐labelled NHCs bound to PdNPs of 3.7 nm. The observation of these very broad KS resonances was facilitated by using Car–Purcell–Meiboom–Gill (CPMG) echo train acquisition NMR experiments.
On the Reactions of Thiols, Sulfenic Acids, and Sulfinic Acids with Hydrogen Peroxide
Authors: Chauvin Jean‐Philippe R. , Pratt Derek A. 
Published: December 2016

AbstractThe reaction of thiols with H2O2 is central to many processes essential to life, from protein folding to redox signaling. The initial products are assumed to be sulfenic acids, but their observation, and the kinetic and mechanistic characterization of their subsequent reactions, has proven challenging. The introduction of a 9‐fluorotriptycene substituent enabled the use of 19F NMR to directly monitor the reaction of a thiol with H2O2 to yield a sulfenic acid, and its subsequent oxidation to sulfinic and sulfonic acids. The oxidations are specific base catalyzed, as revealed by the lack of isotope effects and the dependence of the kinetics on pH but not buffer concentration.
Optimization of thermopressing conditions for the production of binderless boards from a coriander twin‐screw extrusion cake
Authors: Uitterhaegen E. , Labonne L. , Merah O. , Talou T. , Ballas S. , Véronèse T. , Evon Ph. 
Published: December 2016

ABSTRACTA deoiled press cake resulting from twin‐screw extrusion of coriander fruits was used as a raw material for the production of self‐bonded boards. The operating parameters for thermopressing were varied and include the applied pressure (19.6–39.2 MPa), molding time (60–300 s), and molding temperature (155–205 °C). The optimized process conditions (21.6 MPa, 300 s, 205 °C) resulted in a board with a density of 1323 kg/m3, a flexural strength of 23 MPa, a modulus of elasticity of 4.4 GPa, and a thickness swelling of 31%. The thickness swelling was effectively reduced to 20% through the application of a heat treatment at 200 °C after thermopressing. A variation of the moisture content of the press cake between 3 and 8% showed that increased moisture contents do not lead to improved mechanical properties of the resulting board and further induce internal fracturing of the board during thermopressing. The manufactured binderless boards may act as environmentally friendly alternatives to commercial wood‐based boards such as oriented strand board and particleboard. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44650.
Influence of water on phase transition and rheological behavior of cellulose/ionic liquid/water ternary systems
Authors: Lee Young Jae , Kwon Mi Kyung , Lee Sung Jun , Jeong Sang Won , Kim Hyun‐Chul , Oh Tae Hwan , Lee Se Geun 
Published: December 2016

ABSTRACTThe influence of water content on liquid crystalline (LC) gel formation and the rheological behavior of a ternary microcrystalline cellulose (MCC)/1‐ehtyl‐3‐methylimidazolium acetate (EmimAc)/water system was investigated using polarized optical microscopy (POM) and rheometry. POM indicated that the distinct water content range for forming a fully anisotropic LC gel with 14 wt % MCC was 4–10 wt %. Adding water to the MCC/EmimAc system resulted in enhanced complex viscosity and storage and loss moduli, and ultimately LC gel formation. Comparison of creep compliance vs. time revealed that the system without water showed representative viscoelastic behavior, while the time dependence of creep compliance disappeared as the water content increased, suggesting elastic‐solid behavior. Additionally, hydrogen bonding between cellulose and EmimAc weakened as water content increased, whereas the intra‐ and intermolecular hydrogen bonds of cellulose became stronger because of strong self‐association. This strong bonding caused aggregation, chain entanglement, and self‐supporting LC gel network formation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44658.
Two selective HPTLC methods for determination of some angiotensin II receptor antagonists in tablets and biological fluids
Authors: Salah Gamal A. , Abd El‐Wadood Hanaa M. , Khairy Mohamed , Khorshed Ahmed A. 
Published: December 2016

AbstractTwo simple, selective, precise and highly sensitive high‐performance thin‐layer chromatography (HPTLC) methods have been developed and validated for analysis of five angiotensin II receptor antagonists, namely losartan, irbesartan valsartan, candesartan and olmesartan, which are widely used in clinical practice. HPTLC of the drugs was performed on pre‐coated silica gel HPTLC plates 60 F254 by development using a mobile phase composed of chloroform–acetone–glacial acetic acid (7.8:1.5:0.7m v/v/v), which was suitable for all of the studied drugs. The first method depended on utilizing reflectance/fluorescence mode for detection while the second method depended on using 2,3,5,6‐tetrachloro‐1,4‐benzoquinone as spraying reagent for the first time to form orange spots scanned at 460 nm. A good linear relationship was obtained over the concentration ranges of 1.2–60 and 360–3000 ng/band while detection and quantification limits were in the ranges of 0.07–0.43, 45.2–140.49 and 0.21–1.29, 137.05–425.74 ng/band for reflectance/fluorescence and reflectance/absorbance methods respectively. The developed methods were applied successfully for their determination in tablets and spiked human plasma for reflectance/fluorescence method with good accuracy and precision, and so can be applied in the pharmacokinetic and bioavailability studies.
Chemical Variability of Ivoirian Xylopia rubescens Leaf Oil
Authors: Yapi Thierry Acafou , Boti Jean Brice , Tonzibo Zanahi Félix , Ahibo Coffy Antoine , Bighelli Ange , Casanova Joseph , Tomi Félix 
Published: December 2016

Forty‐two essential oil samples were isolated from leaves of Xylopia rubescens harvested in three forests of Southern Ivory Coast. All the samples have been submitted to GC‐FID and the retention indices (RIs) of individual components have been measured on two capillary columns of different polarity. In addition, 20 oil samples, selected on the basis of their chromatographic profile, were also analyzed by 13C‐NMR and 24 components (78.0 – 92.4% of the whole compositions) have been identified. The content of the main components varied drastically from sample to sample: furanoguaia‐1,4‐diene (5.7 – 54.1%), furanoguaia‐1,3‐diene (1.1 – 10.5%), (8Z,11Z,14Z)‐heptadeca‐8,11,14‐trien‐2‐one (4.3 – 16.0%), and (E)‐β‐caryophyllene (1.7 – 17.3%). Hierarchical cluster and principal components analysis of the 42 oil compositions allowed the distinction of two well‐differentiated groups of unequal importance within the oil samples. Oil samples of the main group (Group II) contained mainly furanoguaia‐1,4‐diene (mean [M] = 43.1%; standard deviation [SD] = 3.2%) while furanoguaia‐1,3‐diene (M = 8.4%; SD = 0.9%) and (8Z,11Z,14Z)‐heptadeca‐8,11,14‐trien‐2‐one (M = 7.1%; SD = 1.5%) were present at appreciable contents. The composition of Group I was dominated by furanoguaia‐1,4‐diene (M = 17.0%; SD = 8.5%), (8Z,11Z,14Z)‐heptadeca‐8,11,14‐trien‐2‐one (M = 10.2%; SD = 2.4%) and (E)‐β‐caryophyllene (M = 9.5%; SD = 5.3%).
Three New Iridoid Glycosides from the Aerial Parts of Asperula involucrata
Authors: Kırmızıbekmez Hasan , Tiftik Kubilay , Kúsz Norbert , Orban‐Gyapai Orsolya , Zomborszki Zoltán Péter , Hohmann Judit 
Published: December 2016

Three new iridoid glycosides, named involucratosides A – C (1 – 3), were isolated from the H2O subextract of crude MeOH extract prepared from the aerial parts of Asperula involucrata along with a known iridoid glycoside (adoxoside), three flavone glycosides (apigenin 7‐O‐β‐glucopyranoside, luteolin 7‐O‐β‐glucopyranoside, apigenin 7‐O‐rutinoside) as well as two phenolic acid derivatives (chlorogenic acid and ferulic acid 4‐O‐β‐glucopyranoside). Their chemical structures were established by UV, IR, 1D‐ (1H, 13C and JMOD) and 2D‐ (COSY, HSQC, HMBC and NOESY) NMR experiments and HR‐ESI‐MS. In addition, the crude extract, subextracts and isolates were evaluated for their xanthine oxidase inhibitory and antioxidant activities in in vitro tests. This is the first report on the chemical composition and bioactivities of A. involucrata.
Chemical Composition, Antimicrobial and Insecticidal Activities of Flowers Essential Oils of Alpinia zerumbet (Pers.) B.L.Burtt & R.M.Sm. from Martinique Island
Authors: Kerdudo Audrey , Ellong Emy Njoh , Burger Pauline , Gonnot Vanessa , Boyer Laurent , Chandre Fabrice , Adenet Sandra , Rochefort Katia , Michel Thomas , Fernandez Xavier 
Published: December 2016

Alpinia species, used as ornamental plants and flavoring agents, are renowned for their therapeutic properties and their subsequent use in traditional medicines throughout the world. Alpinia zerumbet (Pers.) B.L.Burtt & R.M.Sm. is the most common Alpinia species encountered in Martinique. Several essential oils (EOs) obtained by hydrodistillation of A. zerumbet flowers collected in various locations on the island at different seasons were analysed to evaluate the influence of the collection period and area on the EOs’ chemical compositions and to assess their bioactivity. A combination of GC‐FID and GC/MS techniques was used to examine the volatile constituents, leading to the identification of a total of 71 components accounting for 97.8 – 99.3% of the respective total GC‐FID areas: among them, nineteen compounds were characterized for the first time in A. zerumbet EOs. The antimicrobial activity of these EOs was assessed against eight bacterial, yeast and fungal strains and two multi‐resistant strains: some significant bacteriostatic and fungistatic activities of A. zerumbet flower oils were evidenced. Finally, an interesting insecticidal activity of the flower EO was highlighted for the first time against Aedes aegypti.
Enhancement of Ag‐Based Plasmonic Photocatalysis in Hydrogen Production from Ammonia Borane by the Assistance of Single‐Site Ti‐Oxide Moieties within a Silica Framework
Authors: Verma Priyanka , Kuwahara Yasutaka , Mori Kohsuke , Yamashita Hiromi 
Published: December 2016

AbstractAg nanoparticles (NPs) have gained great attention owing to their interesting plasmonic properties and efficient catalysis under visible‐light irradiation. In this study, an Ag‐based plasmonic catalyst supported on mesoporous silica with isolated and tetrahedrally coordinated single‐site Ti‐oxide moieties, namely, Ag/Ti‐SBA‐15, was designed with the purpose of utilizing the broad spectral range of solar energy. The Ti‐SBA‐15 support allows the deposition of small Ag NPs with a narrow size distribution. The chemical structure, morphology, and optical properties of the prepared catalyst were characterized by techniques such as UV/Vis, FT extended X‐ray absorption fine structure, and X‐ray photoelectron spectroscopy, field‐emission SEM, TEM, and N2 physisorption studies. The catalytic activity of Ag/Ti‐SBA‐15 in hydrogen production from ammonia borane by hydrolysis was significantly enhanced in comparison with Ag/SBA‐15 without Ti‐oxide moieties and Ag/TiO2/SBA‐15 involving agglomerated TiO2, both in the dark and under light irradiation. Improved electron transfer under light irradiation caused by the creation of heterojunctions between Ag NPs and Ti‐oxide moieties explains the results obtained in the present study.
C3‐Symmetric Boron Lewis Acid with a Cage‐Shape for Chiral Molecular Recognition and Asymmetric Catalysis
Authors: Konishi Akihito , Nakaoka Koichi , Maruyama Hikaru , Nakajima Hideto , Eguchi Tomohiro , Baba Akio , Yasuda Makoto 
Published: December 2016

AbstractChiral Lewis acids play an important role in the precise construction of various types of chiral molecules. Here, a cage‐shaped borate 2 was designed and synthesized as a chiral Lewis acid that possesses a unique C3‐symmetric structure composed of three homochiral binaphthyl moieties. The highly symmetrical structure of 2 with homochirality was clearly elucidated by X‐ray crystallographic analysis. The peculiar chiral environment of 2⋅THF exhibited chiral recognition of some simple amines and a sulfoxide. Moreover, the application of 2⋅THF to hetero‐Diels–Alder reactions as a chiral Lewis‐acid catalyst afforded the enantioselective products, which were obtained through an entropy‐controlled pathway according to the analysis of the relationship between optical yield and reaction temperature. In particular, the robust chiral reaction field of 2⋅THF allowed the first example of an asymmetric hetero‐Diels–Alder reaction with a simple diene despite the requirement of high temperature.
Cell Surface Nano‐modulation for Non‐invasive in vivo Near‐IR Stem Cell Monitoring
Authors: Shin Woo Jung , Shin Seung Won , Yuk Ji Soo , Amornkitbamrung Lunjakorn , Jang Min Su , Song In Hyun , Choi Soon Won , Kang Insung , Lee Jin Young , Bae Hojae , Kang Kyung‐Sun , Um Soong Ho 
Published: December 2016

AbstractA stem cell tracking system is in high demand for the determination of cell destinations and for the validation of cell therapeutic efficacy in regenerative transplantation. To date, near‐infrared (NIR) imaging technology has received considerable attention in cell behavior monitoring, owing to its patient compatibility, easy accessibility and cost effectiveness. Conventionally, in vivo cell tracking has been visualized by direct in‐cell staining with NIR, where it may be achieved by complicated genetic engineering. Such genetic amendment techniques have suffered from serious challenges, which can destroy a cell's metabolism and can accidentally incur unexpected carcinoma. Herein we demonstrate a novel cell nano‐modulation method for noninvasive stem cell monitoring. It is simply achieved by conjugating stem cells with lipid‐supported, NIR‐tagged, polymeric nanoparticles. These engineered cells, which are designated as NIR‐labeled light‐emitting stem cells (LESCs), maintain their biochemical functionality (i.e., differentiation, quantum efficacy, etc.) even after conjugation. LESCs were used for in situ stem cell monitoring at inoculation sites. It is speculated that the LESC technique could provide a new preparative methodology for in vivo cell tracking in advanced diagnostic medicine, where cell behavior is a critical issue.