bluuebunny/crossref_metadata_2025_split huggingface dataset:
Theoretical Design of Multi‐Nitroxyl Organocatalysts with Enhanced Reactivity for Aerobic Oxidation
Authors: Chen Kexian , Jia Lu , Wang Congmin , Yao Jia , Chen Zhirong , Li Haoran 
Published: March 2014

AbstractHigher catalytic performances of N,N′,N′′‐trihydroxyisocyanuric acid (THICA), N,N‐dihydroxypyromellitimide (NDHPI), and N‐hydroxynaphthalimide (NHNI) than that of N‐hydroxyphthalimide (NHPI) have been demonstrated recently in aerobic oxidation. Herein, the rational design of reactive multi‐nitroxyl organocatalysts has been addressed theoretically by using systematic analysis of some important properties and catalytic activities of yet‐to‐be‐synthesized catalysts. Our results show that 1) NHNI and its analogue, similar to THICA, unlike NHPI and others, are unsuitable for solvent‐ or mediator‐free catalysis due to their strong intramolecular hydrogen‐bonding interactions; 2) increasing the reactive hydroxyimide groups on the same aromatic ring, or doped N atoms or ionic‐pair groups onto the aromatic ring, can improve catalytic reactivity, whereas appropriate enlargement of conjugated aromatic systems results in unchanged activity; 3) the newly designed catalysts are more active than NHPI and NHNI and have catalytic activities comparable to NDHPI and THICA; 4) the ionic‐pair supported case is suggested to be a very active catalyst, even towards inert propane, and can be used as a novel model catalyst for further improvements. The present work will be helpful in designing reactive hydroxyimide organocatalysts.
Visualization of the Heterogeneity of Cerium Oxidation States in Single Pt/Ce2Zr2Ox Catalyst Particles by Nano‐XAFS
Authors: Ishiguro Nozomu , Uruga Tomoya , Sekizawa Oki , Tsuji Takuya , Suzuki Motohiro , Kawamura Naomi , Mizumaki Masaichiro , Nitta Kiyofumi , Yokoyama Toshihiko , Tada Mizuki 
Published: March 2014

AbstractThe cerium oxidation states in single catalyst particles of Pt/Ce2Zr2Ox (x=7 to 8) were investigated by spatially resolved nano X‐ray absorption fine structure (nano‐XAFS) using an X‐ray nanobeam. Differences in the distribution of the Ce oxidation states between Pt/Ce2Zr2Ox single particles of different oxygen compositions x were visualized in the obtained two‐dimensional X‐ray fluorescent (XRF) mapping images and the Ce LIII‐edge nano X‐ray absorption near‐edge structure (nano‐XANES) spectra.
Understanding the Photochemical Pathway of In Vitro Target Delivery of Aluminium Phthalocyanine: A Mechanistic Approach Using Radical Reaction Chemistry
Authors: Akpe Victor , Vernet Erik , Madu Christian , Obirai Joseph C. , Brismar Hjalmar 
Published: March 2014

AbstractA classical dye, aluminium phthalocyanine (AlPc), is used to study the photochemical processes involved in the chromophore‐assisted laser inactivation technique. Both cell‐free and cell‐based systems are investigated by novel methods and radical reaction chemistry. Findings on the photochemical pathways in two models representing cell‐free and a cell‐based systems are reported. In the cell‐free system, the unsubstituted, free, fluorescence‐active photosensitiser AlPc recovers its fluorescence signal by means of phosphorescence through a reversible photobleaching process. In the cell‐based system, photoactivation of substituted AlPc conjugated to an antibody results in the loss of fluorescence signal at the area examined. Reinjection of the AlPc‐conjugated antibodies restores the fluorescence signal.
Direct Synthesis of Phenol from Benzene by PdVOx Nanoparticles Using Molecular Oxygen
Authors: Shang Sensen , Yang Hua , Li Jun , Chen Bo , Lv Ying , Gao Shuang 
Published: March 2014

AbstractNovel PdVOx nanoparticles (NPs) prepared by a one‐pot hydrogenation method are reported. X‐ray diffraction, X‐ray photoelectron spectroscopy, transmission electron microscopy, and UV/Vis spectroscopy were performed to characterize the PdVOx NPs. The NPs catalyzed benzene directly to phenol in 5.2 % yield with more than 99 % selectivity using O2 as the sole oxidant.
Synthesis and Application of Carbonated Fatty Acid Esters from Carbon Dioxide Including a Life Cycle Analysis
Authors: Schäffner Benjamin , Blug Matthias , Kruse Daniela , Polyakov Mykola , Köckritz Angela , Martin Andreas , Rajagopalan Prasanna , Bentrup Ursula , Brückner Angelika , Jung Sebastian , Agar David , Rüngeler Bettina , Pfennig Andreas , Müller Karsten , Arlt Wolfgang , Woldt Benjamin , Graß Michael , Buchholz Stefan 
Published: March 2014

AbstractCarbon dioxide can be used in various ways as a cheap C1 source. However, the utilization of CO2 requires energy or energy‐rich reagents, which leads to further emissions, and therefore, diminishes the CO2‐saving potential. Therefore, life cycle assessment (LCA) is required for each process that uses CO2 to provide valid data for CO2 savings. Carbon dioxide can be incorporated into epoxidized fatty acid esters to provide the corresponding carbonates. A robust catalytic process was developed based on simple halide salts in combination with a phase‐transfer catalyst. The CO2‐saving potential was determined by comparing the carbonates as a plasticizer with an established phthalate‐based plasticizer. Although CO2 savings of up to 80 % were achieved, most of the savings arose from indirect effects and not from CO2 utilization. Furthermore, other categories have been analyzed in the LCA. The use of biobased material has a variety of impacts on categories such as eutrophication and marine toxicity. Therefore, the benefits of biobased materials have to be evaluated carefully for each case. Finally, interesting properties as plasticizers were obtained with the carbonates. The volatility and water extraction could be improved relative to the epoxidized system.
Amphiphilic and Phase‐Separable Ionic Liquids for Biomass Processing
Authors: Holding Ashley J. , Heikkilä Mikko , Kilpeläinen Ilkka , King Alistair W. T. 
Published: March 2014

AbstractOne main limiting factor for the technoeconomics of future bioprocesses that use ionic liquids (ILs) is the recovery of the expensive and potentially toxic IL. We have demonstrated a new series of phase‐separable ionic liquids, based on the hydrophobic tetraalkylphosphonium cation ([PRRRR]+), that can dissolve lignin in the neat state but also hemicellulose and high‐purity cellulose in the form of their electrolyte solutions with dipolar aprotic solvents. For example, the IL trioctylmethylphosphonium acetate ([P8881][OAc]) was demonstrated to dissolve up to 19 wt % of microcrystalline cellulose (MCC) at 60 °C with the addition of 40 wt % of DMSO. It was found that the MCC saturation point is dependent on the molar ratio of DMSO and IL in solution. At the optimum saturation, a ∼1:1 molar ratio of [P8881][OAc] to anhydroglucose units is observed, which demonstrates highly efficient solvation. This is attributed to the positive contribution that these more amphiphilic cation–anion pairs provide, in the context of the Lindman hypothesis. This effective dissolution is further illustrated by solution‐state HSQC NMR spectroscopy on MCC. Finally, it is also demonstrated that these electrolytes are phase separable by the addition of aqueous solutions. The addition of 10 % NaOAc solution allows a near quantitative recovery of high‐purity [P8881][OAc]. However, increased volumes of aqueous solution reduced the recovery. The regenerated material was found to partially convert into the cellulose II crystalline polymorph.
Influence of Structural Variations in Push–Pull Zinc Porphyrins on Photovoltaic Performance of Dye‐Sensitized Solar Cells
Authors: Yi Chenyi , Giordano Fabrizio , Cevey‐Ha Ngoc‐Le , Tsao Hoi Nok , Zakeeruddin Shaik M. , Grätzel Michael 
Published: March 2014

AbstractWe designed and synthesized two new zinc porphyrin dyes for dye‐sensitized solar cells (DSCs). Subtle molecular structural variation in the dyes significantly influenced the performance of the DSC devices. By utilizing these dyes in combination with a cobalt‐based redox electrolyte using a photoanode made of mesoporous TiO2, we achieved a power conversion efficiency (PCE) of up to 12.0 % under AM 1.5 G (100 mW cm−2) simulated solar light. Moreover, we obtained a high PCE of 6.4 % for solid‐state dye‐sensitized solar cells by using 2,2′,7,7′‐tetrakis‐(N,N‐di‐p‐methoxyphenylamine)‐9,9′‐spirobifluorene as a hole‐transporting material.
Uncovering Cryptic Glycan Markers in Multiple Sclerosis (MS) and Experimental Autoimmune Encephalomyelitis (EAE)
Authors: Wang Denong , Bhat Roopa , Sobel Raymond A. , Huang Wei , Wang Lai‐Xi , Olsson Tomas , Steinman Lawrence 
Published: March 2014

Abstract

Preclinical Research

Using an integrated antigen microarray approach, we observed epitope‐spreading of autoantibody responses to a variety of antigenic structures in the cerebrospinal fluid (CSF) of patients with multiple sclerosis (MS) and in the serum of mice with experimental autoimmune encephalomyelitis (EAE). These included previously described protein‐ and lipid‐based antigenic targets and newly discovered autoimmunogenic sugar moieties, notably, autoantibodies specific for the oligomannoses in both MS patient CSF and the sera of mice with EAE. These glycans are often masked by other sugar moieties and belong to a class of cryptic autoantigens. We further determined that these targets are highly expressed on multiple cell types in MS and EAE lesions. Co‐immunization of SJL/J mice with a Man9‐KLH conjugate at the time of EAE induction elicited highly significant levels of anti‐Man9‐cluster autoantibodies. Nevertheless, this anti‐glycan autoantibody response was associated with a significantly reduced clinical severity of EAE. The potential of these cryptic glycan markers and targeting antibodies for diagnostic and therapeutic interventions of neurological disorders has yet to be explored.
Vertical transmission of fungal endophytes is widespread in forbs
Authors: Hodgson Susan , de Cates Catherine , Hodgson Joshua , Morley Neil J. , Sutton Brian C. , Gange Alan C. 
Published: March 2014

AbstractTo date, it has been thought that endophytic fungi in forbs infect the leaves of their hosts most commonly by air‐borne spores (termed “horizontal transmission”). Here, we show that vertical transmission from mother plant to offspring, via seeds, occurs in six forb species (Centaurea cyanus, C. nigra, Papaver rhoeas, Plantago lanceolata, Rumex acetosa, and Senecio vulgaris), suggesting that this may be a widespread phenomenon. Mature seeds were collected from field‐grown plants and endophytes isolated from these, and from subsequent cotyledons and true leaves of seedlings, grown in sterile conditions. Most seeds contain one species of fungus, although the identity of the endophyte differs between plant species. Strong evidence for vertical transmission was found for two endophyte species, Alternaria alternata and Cladosporium sphaerospermum. These fungi were recovered from within seeds, cotyledons, and true leaves, although the plant species they were associated with differed. Vertical transmission appears to be an imperfect process, and germination seems to present a bottleneck for fungal growth. We also found that A. alternata and C. sphaerospermum occur on, and within pollen grains, showing that endophyte transmission can be both within and between plant generations. Fungal growth with the pollen tube is likely to be the way in which endophytes enter the developing seed. The fact that true vertical transmission seems common suggests a more mutualistic association between these fungi and their hosts than has previously been thought, and possession of endophytes by seedling plants could have far‐reaching ecological consequences. Seedlings may have different growth rates and be better protected against herbivores and pathogens, dependent on the fungi that were present in the mother plant. This would represent a novel case of trans‐generational resistance in plants.
Immobilization of 1,5,7‐Triazabicyclo[4.4.0]dec‐5‐ene on Magnetic γ‐Fe2O3 Nanoparticles: A Highly Recyclable and Efficient Nanocatalyst for the Synthesis of Organic Carbonates
Authors: Wu Liqiang , Tian Shuanbao 
Published: March 2014

Abstract1,5,7‐Triazabicyclo[4.4.0]dec‐5‐ene was immobilized on magnetic γ‐Fe2O3 nanoparticles as a magnetic nanocatalyst. The nanoparticle reagent was obtained with good loading levels and has been successfully used for the efficient and selective synthesis of organic carbonates by the direct condensation of alcohols and diethyl carbonate. The catalyst is quantitatively recovered by an external magnet and can be reused for six cycles with almost consistent activity.
{Cu2+–Co3+–Cu2+} and {Cu2+–Fe3+–Cu2+} Heterobimetallic Complexes and Their Catalytic Properties
Authors: Srivastava Sumit , Ali Afsar , Tyagi Adish , Gupta Rajeev 
Published: March 2014

AbstractWe report on the heterobimetallic complexes {Cu+–Co3+–Cu+} (3), {Cu+–Fe3+–Cu+} (4), {Cu2+–Co3+–Cu2+} (5), and {Cu2+–Fe3+–Cu2+} (6) and show their catalytic applications in the oxidation of hindered phenols and the oxidative coupling of terminal alkynes. The former reaction produces C–C‐coupled and dealkylated products, whereas the latter leads to the homo‐ and heterocoupling of terminal alkynes. The facile redox interconversion between Cu+ and Cu2+ for the secondary metal ions in these heterobimetallic complexes appears to be essential for the observed catalysis, and an important design aspect is better substrate accessibility and the use of molecular oxygen as the sole oxidant.
Electrochemical Biosensors for the Determination of Cardiovascular Markers: a Review
Authors: Pedrero María , Campuzano Susana , Pingarrón José M. 
Published: March 2014

AbstractNowadays there is a growing interest in the development of devices for the fast and reliable detection and quantification of biomarkers associated with cardiovascular diseases (CVDs). The main objective is not only an early diagnosis of these diseases but also predicting the risk that an individual can suffer CVD. Electrochemical biosensors can play a key role in the development of low cost, portable and rapid sensing platforms for this purpose. This review discusses critically the state of the art in the development, applications and potential suitability of electrochemical biosensors for the determination of cardiovascular biomarkers as well as the required characteristics that these sensors should fulfill to be finally accepted in the clinical community.
Application of surface complexation models to anion adsorption by natural materials
Authors: Goldberg Sabine 
Published: March 2014

Abstract

Various chemical models of ion adsorption are presented and discussed. Chemical models, such as surface complexation models, provide a molecular description of anion adsorption reactions using an equilibrium approach. Two such models, the constant capacitance model and the triple layer model, are described in the present study. Characteristics common to all the surface complexation models are equilibrium constant expressions, mass and charge balances, and surface activity coefficient electrostatic potential terms. Methods for determining parameter values for surface site density, capacitances, and surface complexation constants also are discussed. Spectroscopic experimental methods of establishing ion adsorption mechanisms include vibrational spectroscopy, nuclear magnetic resonance spectroscopy, electron spin resonance spectroscopy, X-ray absorption spectroscopy, and X-ray reflectivity. Experimental determinations of point of zero charge shifts and ionic strength dependence of adsorption results and molecular modeling calculations also can be used to deduce adsorption mechanisms. Applications of the surface complexation models to heterogeneous natural materials, such as soils, using the component additivity and the generalized composite approaches are described. Emphasis is on the generalized composite approach for predicting anion adsorption by soils. Continuing research is needed to develop consistent and realistic protocols for describing ion adsorption reactions on soil minerals and soils. The availability of standardized model parameter databases for use in chemical speciation–transport models is critical. Environ Toxicol Chem 2014;33:2172–2180. Published 2014 Wiley Periodicals Inc. on behalf of SETAC. This article is a US Government work and as such, is in the public domain in the United States.
Design and analysis of an angular‐segmented full‐mobility visible light communications receiver
Authors: Burton Andrew , Ghassemlooy Zabih , Rajbhandari Sujan , Liaw Shien‐Kuei 
Published: March 2014

ABSTRACTThis paper presents the concept, design and analysis for a visible light communications receiver utilising the angular and spatial diversity in order to achieve full mobility and protection from signal blocking in a typical home/office environment. The proposed receiver uses seven sub‐receivers, each dedicated to an independent viewing angle and direction. Employing selection combining, the receiver with the strongest signal is used for the communications channel. Full performance evaluation and numerical analysis of the proposed system have been performed in MATLAB and compared to that of a single receiver. The received power, impulse response, corresponding signal‐to‐noise ratios and root‐mean‐square delay spread are also investigated. Copyright © 2014 John Wiley & Sons, Ltd.
Atypical presentation of Eagle syndrome with hypoglossal nerve palsy and Horner syndrome
Authors: Bensoussan Yael , Letourneau–Guillon Laurent , Ayad Tareck 
Published: March 2014

ABSTRACTBackgroundMany nerve injuries have been associated with Eagle syndrome. The cranial nerves V, VII, IX, and X have been reported to be injured by the elongated styloid process in this syndrome.MethodsWe describe a case of Eagle syndrome with atypical symptoms of hypoglossal nerve palsy and Horner syndrome.ResultsA 56‐year‐old woman presented with right hypoglossal nerve palsy, right Horner syndrome, right neck pain, and symptoms mimicking transient cerebral ischemia. An angioscan showed elongated styloid process bilaterally with the right process compressing the right carotid artery causing a 75% stenosis. After an en bloc resection of the right styloid process, there were no further episodes of paresthesias. The neck pain completely disappeared, as well as the Horner syndrome. As for the hemitongue, the fasciculations disappeared but the atrophy remained.ConclusionThis is the first Eagle syndrome case report describing a motor paralysis of a cranial nerve. © 2014 Wiley Periodicals, Inc. Head Neck 36: E136–E138, 2014
Acute prediction of laryngeal outcome during thyroid surgery by electromyographic laryngeal monitoring
Authors: Pavier Yoann , Saroul Nicolas , Pereira Bruno , Tauveron Igor , Gilain Laurent , Mom Thierry 
Published: March 2014

ABSTRACTBackgroundThe purpose of this study was to evaluate the contribution of laryngeal intraoperative nerve monitoring (IONM) during thyroidectomy in predicting postoperative laryngeal mobility.MethodsBetween 2009 and 2012, 127 patients underwent thyroidectomy, during which 216 recurrent laryngeal nerves were stimulated with suprathreshold stimulations. Laryngeal mobility was examined through direct laryngoscopy. Statistical analysis was performed to determine specificity, sensitivity, negative predictive value (NPV), positive predictive value (PPV), and a threshold value in order to define a intraoperative diagnostic test.ResultsNine patients had a unilateral laryngeal palsy. No bilateral laryngeal palsy was observed. The threshold value to assure the postoperative laryngeal mobility is 280 μV. For this value, specificity was 94.06%, sensitivity 100%, NPV 100%, and PPV 47.83%.ConclusionLaryngeal IONM can predict a favorable outcome of laryngeal mobility in cases in which the response exceeds 280 μV. Under this value, the risk of palsy is about 50% suggesting a staged surgery. © 2014 Wiley Periodicals, Inc. Head Neck 37: 835–839, 2015
Cardiovascular pharmacodynamics of donepezil hydrochloride on the PR and QT intervals in patients with dementia
Authors: Igeta Hirofumi , Suzuki Yutaro , Tajiri Misuzu , Someya Toshiyuki 
Published: March 2014

ObjectiveAlthough several case reports suggested that donepezil hydrochloride can induce bradycardia or atrioventricular block, the details remain unclear. We implemented a study of the impact of donepezil hydrochloride administration on PR, RR, and QT intervals.MethodsThe subjects were 18 patients who were diagnosed with either dementia or cognitive disorder (DSM‐IV‐TR) and were hospitalized between January 2011 and December 2012. After hospitalization, they were treated with donepezil hydrochloride. Clinical parameters and electrocardiograms before and after the administration of donepezil hydrochloride were retrieved from the patients' medical records.ResultsAfter the administration of donepezil hydrochloride, the mean PR interval significantly increased from 177.3 ± 30.9 to 186.8 ± 38.4 ms (p < 0.001). And the mean RR interval also significantly increased from 850.3 ± 112.5 to 886.7 ± 136.4 ms (p = 0.014). The mean difference in the PR interval before and after the administration of donepezil hydrochloride was 9.5 ± 17.1 (range = −21.0–44.0) ms. The QT intervals were unaffected by the administration of donepezil hydrochloride.ConclusionsCare should be taken when administering donepezil to patients with atrioventricular block, or patients taking other drugs that can prolong the PR interval. Copyright © 2014 John Wiley & Sons, Ltd.
An Overview of Interfacial Radiation Chemistry in Nuclear Technology
Authors: Jonsson Mats 
Published: March 2014

AbstractInterfacial radiation chemistry is of key importance in nuclear technology because most materials in the vicinity of radioactive materials in nuclear power plants, reprocessing plants, and repositories for nuclear waste are exposed to ionizing radiation. Corrosion is a crucial issue for the long‐term performance and safety of these installations. Nevertheless, this field is still fairly undeveloped. In this paper, the current state of the art with particular focus on reactions between aqueous radiolysis products and metal or metal oxide surfaces is discussed. The general reactivity of hydrogen peroxide and the hydroxyl radical towards oxide surfaces is discussed on the basis of recent experimental results and DFT calculations. More specific discussions on radiation‐induced surface processes in a future geological repository for spent nuclear fuel are given as relevant examples. This includes radiation‐induced dissolution of spent nuclear fuel in contact with groundwater, radiation‐induced corrosion of copper, and radiation‐induced alterations of bentonite clay. Current knowledge gaps in these areas are highlighted.
Regression Discontinuity Applications with Rounding Errors in the Running Variable
Authors: Dong Yingying 
Published: March 2014

SummaryMany empirical applications of regression discontinuity (RD) models use a running variable that is rounded and hence discrete, e.g. age in years, or birth weight in ounces. This paper shows that standard RD estimation using a rounded discrete running variable leads to inconsistent estimates of treatment effects, even when the true functional form relating the outcome and the running variable is known and is correctly specified. This paper provides simple formulas to correct for this discretization bias. The proposed approach does not require instrumental variables, but instead uses information regarding the distribution of rounding errors, which is easily obtained and often close to uniform. Bounds can be obtained without knowing the distribution of the rounding error. The proposed approach is applied to estimate the effect of Medicare on insurance coverage in the USA, and to investigate the retirement‐consumption puzzle in China, utilizing the Chinese mandatory retirement policy. Copyright © 2014 John Wiley & Sons, Ltd.