bluuebunny/crossref_metadata_2025_split huggingface dataset:
Identifying errors in dust models from data assimilation
Authors: Pope R. J. , Marsham J. H. , Knippertz P. , Brooks M. E. , Roberts A. J. 
Published: August 2016

AbstractAirborne mineral dust is an important component of the Earth system and is increasingly predicted prognostically in weather and climate models. The recent development of data assimilation for remotely sensed aerosol optical depths (AODs) into models offers a new opportunity to better understand the characteristics and sources of model error. Here we examine assimilation increments from Moderate Resolution Imaging Spectroradiometer AODs over northern Africa in the Met Office global forecast model. The model underpredicts (overpredicts) dust in light (strong) winds, consistent with (submesoscale) mesoscale processes lifting dust in reality but being missed by the model. Dust is overpredicted in the Sahara and underpredicted in the Sahel. Using observations of lighting and rain, we show that haboobs (cold pool outflows from moist convection) are an important dust source in reality but are badly handled by the model's convection scheme. The approach shows promise to serve as a useful framework for future model development.
Consequences of inhibition of mixed‐layer deepening by the West India Coastal Current for winter phytoplankton bloom in the northeastern Arabian Sea
Authors: Vijith V. , Vinayachandran P. N. , Thushara V. , Amol P. , Shankar D. , Anil A. C. 
Published: August 2016

AbstractThe intense winter phytoplankton bloom during November–February in the northeastern Arabian Sea (NEAS) was thought, until recently, to be controlled only by a convective deepening of the mixed layer (ML) owing to cool and dry northeasterlies. But a recent study has shown that the deepening of the ML in the southern NEAS is inhibited by the poleward advection of low‐salinity water from the south by the West India Coastal Current (WICC). Using an Ocean General Circulation Model coupled with an ecosystem model, we investigate the consequences of the inhibition of mixed‐layer deepening for winter phytoplankton bloom in the NEAS. We show that, during the winter monsoon, the shallow ML inhibits the entrainment of nutrients in the southern NEAS. Strong (weak) positive nitrate tendency in the northern (southern) NEAS seen in the model during the winter monsoon is maintained by strong (weak) entrainment. As a result, the chlorophyll integrated to 200 m depth from the surface is lower in the southern NEAS than in the northern NEAS. The inhibition of mixed‐layer deepening in the south affects the size‐based distribution of small and large phytoplankton, nutrient limitation terms and growth rate, and their elemental composition. The WICC, which inhibits the deepening of the ML and affects the winter bloom in the NEAS, is driven by coastal Kelvin waves generated by remote winds. This paper demonstrates a mechanism by which remotely forced coastal Kelvin waves impact the biology in the north Indian Ocean.
Masculine Ideology, Sexual Communication, and Sexual Self‐Efficacy Among Parenting Adolescent Couples
Authors: Norton Melanie K. , Smith Megan V. , Magriples Urania , Kershaw Trace S. 
Published: August 2016

AbstractThis study examined the relationship between traditional masculine role norms (status, toughness, anti‐femininity) and psychosocial mechanisms of sexual risk (sexual communication, sexual self‐efficacy) among young, low‐income, and minority parenting couples. Between 2007 and 2011, 296 pregnant adolescent females and their male partners were recruited from urban obstetrics clinics in Connecticut. Data regarding participants' beliefs in masculine role norms, frequency of general sex communication and sexual risk communication, and sexual self‐efficacy were collected via computer‐assisted self‐interviews. Generalized estimating equation (GEE) models were used to test for actor effects (whether a person's masculine role norms at baseline influence the person's own psychosocial variables at 6‐month follow‐up) and partner effects (whether a partner's masculine role norms at baseline influence an actor's psychosocial variables at 6‐month follow‐up). Results revealed that higher actor status norms were significantly associated with more sexual self‐efficacy, higher actor toughness norms were associated with less sexual self‐efficacy, and higher actor anti‐femininity norms were significantly associated with less general sex communication, sexual risk communication, and sexual self‐efficacy. No partner effects were found. These results indicate a need for redefining masculine role norms through family centered approaches in pregnant or parenting adolescent couples to increase sexual communication and sexual self‐efficacy. Further research is needed to understand partner effects in the context of a relationship and on subsequent sexual risk behavior.
Targeted Covalent Inhibitors for Drug Design
Authors: Baillie Thomas A. 
Published: August 2016

AbstractIn contrast to the traditional mechanism of drug action that relies on the reversible, noncovalent interaction of a ligand with its biological target, a targeted covalent inhibitor (TCI) is designed such that the initial, reversible association is followed by the formation of a covalent bond between an electrophile on the ligand and a nucleophilic center in the protein. Although this approach offers a variety of potential benefits (high potency and extended duration of action), concerns over the possible toxicological consequences of protein haptenization have hindered the development of the TCI concept. Recently, approaches to mitigate the risk of serious adverse reactions to this new class of agent have emerged, thus stimulating interest in the field and leading to authorization of the first cadre of TCIs to be marketed. The covalent inhibitor approach is rapidly gaining acceptance as a valuable tool in drug discovery, and is poised to make a major impact on the design of enzyme inhibitors and receptor modulators.
The synthesis of metal–organic framework Al‐MIL‐53‐derived Brønsted acid catalyst and its application in the Mannich reaction
Authors: Miao Zongcheng , Qi Chao , Wang Liangshi , Wensley Allison M. , Luan Yi 
Published: August 2016

A metal–organic framework Al‐MIL‐53‐NH2‐derived Brønsted acid catalyst (Al‐MIL‐53‐RSO3H) has been synthesized employing a post‐synthetic modification strategy under mild conditions. The Al‐MIL‐53‐RSO3H catalyst was successfully utilized in the nitro‐Mannich reaction taking advantage of its strong Brønsted acidity. Good to excellent yields of Mannich adducts were achieved for a variety of acylimine substrates in the presence of 0.1 mol% Al‐MIL‐53‐RSO3H. Furthermore, the Al‐MIL‐53‐RSO3H catalyst can be recycled five times without decreasing the yield and selectivity of Mannich adducts.
Aggregation‐Induced Emission and Aggregation‐Promoted Photo‐oxidation in Thiophene‐Substituted Tetraphenylethylene Derivative
Authors: Zhu Linna , Wang Rui , Tan Luxi , Liang Xianfeng , Zhong Cheng , Wu Fei 
Published: August 2016

AbstractAggregation‐induced emission combined with aggregation‐promoted photo‐oxidation has been reported only in two works quite recently. In fact, this phenomenon is not commonly observed for AIE‐active molecules. In this work, a new tetraphenylethylene derivative (TPE‐4T) with aggregation‐induced emission (AIE) and aggregation‐promoted photo‐oxidation was synthesized and investigated. The pristine TPE‐4T film exhibits strong bluish‐green emission, which turns to quite weak yellow emission after UV irradiation. Interestingly, after solvent treatment, the weakly fluorescent intermediate will become bright‐yellow emitting. Moreover, the morphology of the TPE‐4T film could be regulated by UV irradiation. The wettability of the TPE‐4T microcrystalline surface is drastically changed from hydrophobic to hydrophilic. This work contributes a new member to the aggregation induced photo‐oxidation family and enriches the photo‐oxidation study of tetraphenylethylene derivatives.
Analysis of predictability of F‐18 fluorodeoxyglucose‐PET/CT in the recurrence of papillary thyroid carcinoma
Authors: Kim Suk Kyeong , So Young , Chung Hyun Woo , Yoo Young Bum , Park Kyung Sik , Hwang Tae Sook , Kim Bokyung , Lee Won Woo 
Published: August 2016

AbstractWhether preoperative F‐18 fluorodeoxyglucose (FDG)‐positron emission tomography/computed tomography (PET/CT) can predict recurrence of papillary thyroid carcinoma (PTC) remains unclear. Herein, we evaluated the potential of primary tumor FDG avidity for the prediction of tumor recurrence in PTC patients. A total of 412 PTC patients (72 males, 340 females; age: 47.2 ± 12.2 years; range: 17–84 years) who underwent FDG‐PET/CT prior to total thyroidectomy (n = 350), subtotal thyroidectomy (n = 2), or lobectomy (n = 60) from 2007 to 2011 were analyzed. The predictive ability for recurrence was investigated among various clinicopathological factors, BRAFV600E mutation, and preoperative FDG avidity of the primary tumor using Kaplan–Meier (univariate) and Cox proportional hazards regression (multivariate) analyses. Of the 412 patients, 19 (4.6%) experienced recurrence, which was confirmed either by pathology (n = 17) or high serum thyroglobulin level (n = 2), during a mean follow‐up period of 43.9 ± 16.6 months. Of the 412 patients, 237 (57.5%) had FDG‐avid tumors (maximum standardized uptake value, 7.1 ± 7.0; range: 1.6–50.5). Kaplan–Meier analysis revealed that tumor size (P = 0.0054), FDG avidity of the tumor (P = 0.0049), extrathyroidal extension (P = 0.0212), and lymph node (LN) stage (P < 0.0001) were significant predictors for recurrence. However, only LN stage remained a significant predictor in the multivariate analysis (P < 0.0001). Patients with FDG‐avid tumors had higher LN stage (P < 0.0001), larger tumor size (P < 0.0001), and more frequent extrathyroidal extension (P < 0.0001). In conclusion, FDG avidity of the primary tumor in preoperative FDG‐PET/CT could not predict the recurrence of PTC. LN stage was the only identified predictor of PTC recurrence.
H2O2 Generation at a Carbon‐Paste Electrode with Decamethylferrocene in 2‐Nitrophenyloctyl Ether as a Binder: Catalytic Effect of MoS2 Particles
Authors: Jedraszko Justyna , Krysiak Olga , Adamiak Wojciech , Nogala Wojciech , Girault Hubert H. , Opallo Marcin 
Published: August 2016

AbstractThe front cover artwork is provided by the group of Marcin Opallo at the Institute of Physical Chemistry, Polish Academy of Sciences (Warsaw, Poland). The image shows the mechanism of scanning electrochemical microscopy detection of hydrogen peroxide generated at a liquid|liquid interface. Read the full text of the Article at 10.1002/celc.201600242.
The Key Role of U28 in the Aqueous Self‐Assembly of Uranyl Peroxide Nanocages
Authors: Falaise Clément , Nyman May 
Published: August 2016

AbstractFor 11 years now, the structural diversity and aesthetic beauty of uranyl–peroxide capsules have fascinated researchers from the diverse fields of mineralogy, polyoxometalate chemistry, and nuclear fuel technologies. There is still much to be learned about the mechanisms of the self‐assembly process, and the role of solution parameters including pH, alkali template, temperature, time, and others. Here we have exploited the high solubility of the UO22+/H2O2/LiOH aqueous system to address the effect of the hydroxide concentration. Important techniques of this study are single‐crystal X‐ray diffraction, small‐angle X‐ray scattering, and Raman spectroscopy. Three key phases dominate the solution speciation as a function of time and the LiOH/UO22+ ratio: the uranyl–triperoxide monomer [UO2(O2)3]4−and the two capsules [(UO2)(O2)(OH)]2424−(U24) and [(UO2)(O2)1.5]2828−(U28). When the LiOH/U ratio is around three, U28 forms rapidly and this cluster can be isolated in high yield and purity. This result was most surprising and challenges the hypothesis that alkali templating is the most important determinant in the cluster geometry. Moreover, analogous experiments with KOH, NH4OH, and TEAOH (TEA=tetraethylammonium) also rapidly yield U28, which suggests that U28 is the kinetically favored species. Complete mapping of the pH–time phase space reveals only a narrow window of the U28 dominance, which is why it was previously overlooked as an important kinetic species in this chemical system, as well as others with different counterions.
The Cysteine S‐Alkylation Reaction as a Synthetic Method to Covalently Modify Peptide Sequences
Authors: Calce Enrica , De Luca Stefania 
Published: August 2016

AbstractSynthetic methodologies to chemically modify peptide molecules have long been investigated for their impact in the field of chemical biology. They allow the introduction of biochemical probes useful for studying protein functions, for manipulating peptides with therapeutic potential, and for structure–activity relationship investigations. The commonly used approach was the derivatization of an amino acid side chain. In this regard, the cysteine, for its unique reactivity, has been widely employed as the substrate for such modifications. Herein, we report on methodologies developed to modify the cysteine thiol group through the S‐alkylation reaction. Some procedures perform the alkylation of cysteine derivatives, in order to prepare building blocks to be used during the peptide synthesis, whilst some others selectively modify peptide sequences containing a cysteine residue with a free thiol group, both in solution and in the solid phase.
The Propargyl Rearrangement to Functionalised Allyl‐Boron and Borocation Compounds
Authors: Wilkins Lewis C. , Lawson James R. , Wieneke Philipp , Rominger Frank , Hashmi A. Stephen K. , Hansmann Max M. , Melen Rebecca L. 
Published: August 2016

AbstractA diverse range of Lewis acidic alkyl, vinyl and aryl boranes and borenium compounds that are capable of new carbon–carbon bond formation through selective migratory group transfer have been synthesised. Utilising a series of heteroleptic boranes [PhB(C6F5)2 (1), PhCH2CH2B(C6F5)2 (2), and E‐B(C6F5)2(C6F5)C=C(I)R (R=Ph 3 a, nBu 3 b)] and borenium cations [phenylquinolatoborenium cation ([QOBPh][AlCl4], 4)], it has been shown that these boron‐based compounds are capable of producing novel allyl‐ boron and boronium compounds through complex rearrangement reactions with various propargyl esters and carbamates. These reactions yield highly functionalised, synthetically useful boron substituted organic compounds with substantial molecular complexity in a one‐pot reaction.
Photocontrolled On‐Surface Pseudorotaxane Formation with Well‐Ordered Macrocycle Multilayers
Authors: Schwarz Felix B. , Heinrich Thomas , Kaufmann J. Ole , Lippitz Andreas , Puttreddy Rakesh , Rissanen Kari , Unger Wolfgang E. S. , Schalley Christoph A. 
Published: August 2016

AbstractThe photoinduced pseudorotaxane formation between a photoresponsive axle and a tetralactam macrocycle was investigated in solution and on glass surfaces with immobilized multilayers of macrocycles. In the course of this reaction, a novel photoswitchable binding station with azobenzene as the photoswitchable unit and diketopiperazine as the binding station was synthesized and studied by NMR and UV/Vis spectroscopy. Glass surfaces have been functionalized with pyridine‐terminated SAMs and subsequently with multilayers of macrocycles through layer‐by‐layer self assembly. A preferred orientation of the macrocycles could be confirmed by NEXAFS spectroscopy. The photocontrolled deposition of the axle into the surface‐bound macrocycle‐multilayers was monitored by UV/Vis spectroscopy and led to an increase of the molecular order, as indicated by more substantial linear dichroism effects in angle‐resolved NEXAFS spectra.
A Switchable Gold Catalyst by Encapsulation in a Self‐Assembled Cage
Authors: Jans Anne C. H. , Gómez‐Suárez Adrián , Nolan Steven P. , Reek Joost N. H. 
Published: August 2016

AbstractDinuclear gold complexes have the ability to interact with one or more substrates in a dual‐activation mode, leading to different reactivity and selectivity than their mononuclear relatives. In this contribution, this difference was used to control the catalytic properties of a gold‐based catalytic system by site‐isolation of mononuclear gold complexes by selective encapsulation. The typical dual‐activation mode is prohibited by this catalyst encapsulation, leading to typical behavior as a result of mononuclear activation. This strategy can be used as a switch (on/off) for a catalytic reaction and also permits reversible control over the product distribution during the course of a reaction.
Cephalotanins A–D, Four Norditerpenoids Represent Three Highly Rigid Carbon Skeletons from Cephalotaxus sinensis
Authors: Xu Jin‐Biao , Fan Yao‐Yue , Gan Li‐She , Zhou Yu‐Bo , Li Jia , Yue Jian‐Min 
Published: August 2016

AbstractFour polycyclic norditerpenoids, cephalotanins A–D (1–4) representing three unprecedented carbon skeletons with highly rigid ring systems, were isolated from Cephalotaxus sinensis and structurally characterized by a combination of various methods. Compounds 1 and 2 are new skeletal norditerpenoid trilactones, while 3 and 4 are two norditerpenoids featuring different new carbon skeletons. Biosynthetic pathways for 1–4 were proposed by involving diverse and very fascinating chemical events with the coexisting cephalotane troponoids as the precursors. Compound 1 exhibited good NF‐κB inhibition with an IC50 value of 4.12±0.61 μΜ.
A Germylene/Borane Lewis Pair and the Remarkable C=O Bond Cleavage Reaction toward Isocyanate and Ketone Molecules
Authors: Li Jiancheng , Li Bin , Liu Rui , Jiang Liuyin , Zhu Hongping , Roesky Herbert W. , Dutta Sayan , Koley Debasis , Liu Weiping , Ye Qingsong 
Published: August 2016

AbstractA germylene/borane Lewis pair (2) was prepared from a 1,1‐carboboration of amidinato phenylethynylgermylene (1) by B(C6F5)3. Compound 2 reacted with iPrNCO and (4‐MeOC6H4)C(O)Me, respectively, with cleavage of the C=O double bond. In the first instance, O and iPrNC insert separately into the Ge−B bond to yield a GeBC2O‐heterocycle (3) and a GeBC3‐heterocycle (4). In the second case (4‐MeOC6H4)(Me)C inserts into the Ge−N bond of 2 while O is incorporated in the Ge−B bond to form a Ge‐centered spiroheterocycle (5). The reaction of 2 with tBuNC to give 6, which has almost the same structure as 4, proved the formation of the isonitrile during transformation from 2 and iPrNCO to 3 and 4. The kinetic study of the reaction of 2 and iPrNCO gave evidence of proceeding through a GeBC3O‐heterocycle intermediate. In addition, a DFT study was performed to elucidate the reaction mechanism.
Dental implant customization using numerical optimization design and 3‐dimensional printing fabrication of zirconia ceramic
Authors: Cheng Yung‐Chang , Lin Deng‐Huei , Jiang Cho‐Pei , Lin Yuan‐Min 
Published: August 2016

AbstractThis study proposes a new methodology for dental implant customization consisting of numerical geometric optimization and 3‐dimensional printing fabrication of zirconia ceramic. In the numerical modeling, exogenous factors for implant shape include the thread pitch, thread depth, maximal diameter of implant neck, and body size. Endogenous factors are bone density, cortical bone thickness, and non‐osseointegration. An integration procedure, including uniform design method, Kriging interpolation and genetic algorithm, is applied to optimize the geometry of dental implants. The threshold of minimal micromotion for optimization evaluation was 100 μm. The optimized model is imported to the 3‐dimensional slurry printer to fabricate the zirconia green body (powder is bonded by polymer weakly) of the implant. The sintered implant is obtained using a 2‐stage sintering process. Twelve models are constructed according to uniform design method and simulated the micromotion behavior using finite element modeling. The result of uniform design models yields a set of exogenous factors that can provide the minimal micromotion (30.61 μm), as a suitable model. Kriging interpolation and genetic algorithm modified the exogenous factor of the suitable model, resulting in 27.11 μm as an optimization model. Experimental results show that the 3‐dimensional slurry printer successfully fabricated the green body of the optimization model, but the accuracy of sintered part still needs to be improved. In addition, the scanning electron microscopy morphology is a stabilized t‐phase microstructure, and the average compressive strength of the sintered part is 632.1 MPa.
Entropy Drives Calcium Carbonate Ion Association
Authors: Kellermeier Matthias , Raiteri Paolo , Berg John K. , Kempter Andreas , Gale Julian D. , Gebauer Denis 
Published: August 2016

AbstractThe understanding of the molecular mechanisms underlying the early stages of crystallisation is still incomplete. In the case of calcium carbonate, experimental and computational evidence suggests that phase separation relies on so‐called pre‐nucleation clusters (PNCs). A thorough thermodynamic analysis of the enthalpic and entropic contributions to the overall free energy of PNC formation derived from three independent methods demonstrates that solute clustering is driven by entropy. This can be quantitatively rationalised by the release of water molecules from ion hydration layers, explaining why ion association is not limited to simple ion pairing. The key role of water release in this process suggests that PNC formation should be a common phenomenon in aqueous solutions.
On The Potential of Dynamic Nuclear Polarization Enhanced Diamonds in Solid‐State and Dissolution 13C NMR Spectroscopy
Authors: Bretschneider Christian O. , Akbey Ümit , Aussenac Fabien , Olsen Greg L. , Feintuch Akiva , Oschkinat Hartmut , Frydman Lucio 
Published: August 2016

AbstractThe front cover artwork is provided by the group of Prof. Lucio Frydman from the Weizmann Institute, in collaboration with Dr. Fabien Aussenac and Profs. Amit Ukbey and Hartmut Oschkinat from Bruker Biospin, Aarhus University and the Leibniz Institute, respectively. The image shows aspects of diamond's dynamic nuclear polarization investigated in this study, in particular their use in dissolution MRI and in solid state magic‐angle‐spinning NMR experiments. Read the full text of the article at 10.1002/cphc.201600301.
Channel‐independent 3D‐EXIT chart‐based path scheduling for serially concatenated decoders
Authors: Kayani Atiqa , Khan Asif , Ullah Irfan , Khattak Shahid 
Published: August 2016

SummaryIn this paper a generic method for determining optimal activation cycle scheduling for serially concatenated decoders using three‐dimensional Extrinsic Information Transfer charts is proposed. The complexity of a turbo decoding receiver can be reduced considerably by adopting an optimal activation cycle within the component decoders. However, this optimum scheduled path varies with channel conditions for a given modulation and coding scheme. Thus a real‐time evaluation of the activation path is required, which results in an added computational overhead and storage requirement. Therefore, a channel‐independent method of optimal activation path scheduling using three‐dimensional extrinsic information transfer chart analysis has been proposed where the activation cycle needs to be evaluated once offline and stored as lookup tables as a function of an appropriate compression parameter. The average mutual information of the codeword has been adopted as this compression parameter. It has been demonstrated that the proposed reduced complexity receiver's performance is very close to the more complex conventional fixed activation cycle schemes and superior to the signal to noise ratio‐based dynamic scheduling schemes. Copyright © 2016 John Wiley & Sons, Ltd.