bluuebunny/crossref_metadata_2025 huggingface dataset:
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

The 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

This 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.
Clinical intrafamilial variability in lethal familial neonatal seizure disorder caused by TBC1D24 mutations
Authors: Lozano Reymundo , Herman Kristin , Rothfuss Melanie , Rieger Hillary , Bayrak‐Toydemir Pinar , Aprile Davide , Fruscione Floriana , Zara Federico , Fassio Anna
Published: August 2016

TBC1D24‐related disorders include a wide phenotypic ranging from mild to lethal seizure disorders, non‐syndromic deafness, and composite syndromes such as DOORS (deafness, onychodystrophy, osteodystrophy, mental retardation, and seizures). The TBC1D24 gene has a role in cerebral cortex development and in presynaptic neurotransmission. Here, we present a familial case of a lethal early‐onset epileptic encephalopathy, associated with two novel compound heterozygous missense variants on the TBC1D24 gene, which were detected by exome sequencing. The detailed clinical data of the three siblings is summarized in order to support the variability of the phenotype, severity, and progression of this disorder among these family members. Functional studies demonstrated that the identified novel missense mutations result in a loss of expression of the protein, suggesting a correlation between residual expression, and the disease severity. This indicates that protein expression analysis is important for interpreting genetic results when novel variants are found, as well as for complementing clinical assessment by predicting the functional impact. Further analysis is necessary to delineate the clinical presentation of individuals with TBC1D24 pathogenic variants, as well as to develop markers for diagnosis, prognosis, and potential targeted treatments. © 2016 Wiley Periodicals, Inc.
Targeted Covalent Inhibitors for Drug Design
Authors: Baillie Thomas A.
Published: August 2016

In 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

Aggregation‐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

Whether 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

The 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

For 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

Synthetic 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

A 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

The 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

Dinuclear 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

Four 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

A 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.
Response of Nutrient Release of Periploca sepium Litter to Soil Petroleum Contamination
Authors: Zhang Xiaoxi , Liu Zengwen , Hu Wei
Published: August 2016

The alteration of soil biological and chemical properties caused by petroleum contamination might result in limitations in the nutrient release from plant litter and thus threaten the stability of plant communities. In this study, the foliar litter of Periploca sepium was buried into lightly (petroleum concentration was 15 g kg−1), moderately (30 g kg−1), and seriously (45 g kg−1) contaminated soil for a 1 year decomposition experiment. The dynamics of nutrient release and the final nutrient release rates were determined, and the impacts of petroleum contamination on the release of C, N, P, K, Cu, Zn, Fe, Mn, Ca, and Mg from the litter were assessed. The results indicated that the release of all nutrients was significantly accelerated in the slightly and moderately contaminated soil. In contrast, the release of C, N, P, and K was significantly inhibited in the seriously contaminated soil, while only the Cu release from litter was significantly and simultaneously accelerated. Generally, serious soil petroleum contamination would significantly hinder the overall nutrient release from P. sepium litter; thus, P. sepium could only be utilized in the ecological restoration of contaminated soils with a petroleum concentration lower than 45 g kg−1.
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

This 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

The 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

The 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

In 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.
Neonatal experiences with ethanol intoxication modify respiratory and thermoregulatory plasticity and affect subsequent ethanol intake in rats
Authors: Acevedo María Belén , Macchione Ana Fabiola , Anunziata Florencia , Haymal Olga Beatriz , Molina Juan Carlos
Published: August 2016

Different studies have focused on the deleterious consequences of binge‐like or chronic exposure to ethanol during the brain growth spurt period (third human gestational trimester) that in the rat corresponds to postnatal days (PDs) 3–10. The present study analyzed behavioral and physiological disruptions caused by relatively brief binge‐like exposures (PDs 3, 5, and 7) with an ethanol dose lower (3.0 g/kg) than those frequently employed to examine teratological effects during this stage in development. At PD 9, pups were exposed to ethanol doses ranging between .0–3.0 g/kg and tested in terms of breathing patterns and thermoregulation. At PDs 11 and 12, ethanol intake was examined. The main findings were as follows: i) pre‐exposure to the drug resulted in brief depressions in breathing frequencies and an exacerbated predisposition toward apneic episodes; ii) these effects were not dependent upon thermoregulatory alterations; iii) early ethanol treatment increased initial consumption of the drug which also caused a marked hypothermia that appeared to regulate a subsequent decrement in ethanol consumption; and iv) ethanol exposure retarded overall body growth and even one exposure to the drug (PD 9) was sufficient to reduce brain weights although there were no indications of microcephaly. In conjunction with studies performed during the late gestational period in the rat, the results indicate that relatively brief binge‐like episodes during a critical window of brain vulnerability disrupts the respiratory network and exacerbates initial acceptance of the drug. In addition, ethanol treatments were not found to induce tolerance relative to respiratory and thermal disruptions.
One‐step purification and immobilization of a β‐amino acid aminotransferase using magnetic (M‐PVA) beads
Authors: Dold Sarah‐Marie , Cai Liyin , Rudat Jens
Published: August 2016

Aminotransferases (ATs) received much attention as biocatalyst in the last decades and are utilized for the synthesis of chiral amines, amino alcohols and amino acids. More recently, enzymatic synthesis of enantiopure β‐amino acids is of increasing interest, for their application in peptidomimetics or other drug related compounds. For economic process management it is of major interest to acquire reusable biocatalysts. This is achievable by immobilization of the enzymes. A wide range of immobilization techniques for ATs exists. Two of the most common procedures are entrapment in sol‐gel or calcium‐alginate and alternatively covalent binding to chitosan support. For these traditional immobilization techniques, high amounts of purified enzyme solutions are required which is cost intensive. A major step toward faster and straightforward immobilization is the insertion of affinity tags, like a His‐tag, to the enzyme coding gene. Immobilization on non‐porous polyvinyl magnetic micro beads functionalized with IDA (iminodiacetic acid) leads to a fast and easy one‐step purification and immobilization of a β‐amino acid AT from Variovorax paradoxus. For loading of the functionalized beads, three divalent metal ions (Ni2+, Co2+ and Cu2+) were tested. The best activity was obtained with Ni2+ and almost no activity was detected after loading the beads with Cu2+. The immobilized AT was successfully tested to synthesize several enantiopure β‐amino acids via kinetic resolution. Further examination and characterization of this immobilized AT showed improved stability compared to the crude cell extract. The immobilized AT revealed enhanced pH and thermal stability compared to the crude cell extract. High activity was preserved up to 38 days of storage at 4°C. Moreover, the use of magnetic beads allows an easy and mild recycling of the immobilized enzyme after the reaction, leading to an efficient reuse of the immobilized enzyme, for at least seven cycles.
Response to Professor John Hall's discussion of Hardyniec and Charney's paper, ‘An investigation into the effects of damping and nonlinear geometry models in earthquake engineering analysis’
Authors: Hardyniec Andrew , Charney Finley
Published: August 2016

The discussion presents questions regarding the recommended damping scheme from the discussed paper and provides an alternative recommendation. The discussion also requests further explanation on behavioral differences between models incorporating the P‐delta and corotational approaches that are presented in the paper. Responses to these questions are presented. Copyright © 2016 John Wiley & Sons, Ltd.
Organic contamination in tree swallow (Tachycineta bicolor) nestlings at United States and binational Great Lakes Areas of Concern
Authors: Custer Thomas W. , Custer Christine M. , Dummer Paul M. , Goldberg Diana , Franson J. Christian , Erickson Richard A.
Published: August 2016

Contaminant exposure of tree swallows, Tachycineta bicolor, nesting in 27 Areas of Concern (AOCs) in the Great Lakes basin was assessed from 2010 to 2014 to assist managers and regulators in their assessments of Great Lakes AOCs. Contaminant concentrations in nestlings from AOCs were compared with those in nestlings from nearby non-AOC sites. Polychlorinated biphenyl (PCB) and polybrominated diphenyl ether concentrations in tree swallow nestling carcasses at 30% and 33% of AOCs, respectively, were below the mean concentration for non-AOCs. Polycyclic aromatic hydrocarbon (PAH) concentrations in nestling stomach contents and perfluorinated compound concentrations in nestling plasma at 67% and 64% of AOCs, respectively, were below the mean concentration for non-AOCs. Concentrations of PCBs in nestling carcasses were elevated at some AOCs but modest compared with highly PCB-contaminated sites where reproductive effects have been documented. Concentrations of PAHs in diet were sufficiently elevated at some AOCs to elicit a measurable physiological response. Among AOCs, concentrations of the perfluorinated compound perfluorooctane sulfonate in plasma were the highest on the River Raisin (MI, USA; geometric mean 330 ng/mL) but well below an estimated toxicity reference value (1700 ng/mL). Both PAH and PCB concentrations in nestling stomach contents and PCBs in carcasses were significantly correlated with concentrations in sediment previously reported, thereby reinforcing the utility of tree swallows to assess bioavailability of sediment contamination. Environ Toxicol Chem 2017;36:735–748. Published 2016 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 of America.
Novel D2D resource partitioning and allocation schemes for SC‐FDMA‐based public safety systems
Authors: Park Seung‐Hoon , Kim Jun Suk , Gu Jaheon , Chung Min Young
Published: August 2016

Device‐to‐device (D2D) communication is essential for the provision of the broadcasting service for public safety (PS) terminals in out‐of‐network coverage. A sensing‐based resource‐allocation scheme is desirable, rather than a random approach, for next‐generation, PS systems, so that higher data rates and a massive connectivity can be supported. The half‐duplex and resource collisions are the main design constraints, especially for the single carrier frequency division multiplexing (SC‐FDMA)‐based D2D broadcast system. A novel resource‐allocation scheme is proposed in this paper, whereby the resource partitions are managed adaptively based on sensing results. The system‐level evaluation and analysis results show that the proposed scheme significantly improves upon the overall network performance of the conventional scheme, especially with respect to the resource‐collision rate and the throughput. Copyright © 2016 John Wiley & Sons, Ltd.
Quantifying the effects of Eucalyptus plantations and management on water resources at plot and catchment scales
Authors: Almeida Auro C. , Smethurst Philip J. , Siggins Anders , Cavalcante Rosane B. L. , Borges Norton
Published: August 2016

Our aim was to quantify the effects of forest plantation and management (clear cut or 30% partial harvest) in relation to pasture, on catchment discharge in southeast Rio Grande do Sul state, Brazil. A paired‐catchment approach was implemented in two regions (Eldorado do Sul and São Gabriel municipalities) where discharge was measured for 4 years at three catchments in each region, two of which were predominantly eucalypt plantation (mainly Eucalyptus saligna, rotation of approximately 7–9 years) with native forest and grass in streamside zones. The third catchment was covered with grazed pasture. Weather, soils, canopy interception, groundwater level, tree growth, and leaf area index were also measured.

The 3‐PG process‐based forest productivity model was adapted to predict spatial daily plantation and pasture water balance including precipitation interception, soil evaporation, transpiration, soil moisture, drainage, discharge, and monthly plantation growth. The TOPMODEL framework was used to simulate water pools and fluxes in the catchments.

Discharge was higher under pasture than pre‐harvesting plantation and increased for 1–2 years after complete plantation harvest; this change was less pronounced in the catchments under partial harvest. The ratio of discharge to precipitation before harvesting varied from 7% to 13% in the eucalypt catchments and 28% to 29% under pasture. The ratio increases to 23–24% after total harvest, and to 17% after partial harvesting. The ratio under pasture also increases during this period (to 32–44%) owing to increased precipitation. The baseflow, in relation to total discharge, varied from 28% to 62% under Eucalyptus and from 38% to 43% in the pasture catchments. Hence, eucalypt plantations in these regions can be expected to influence discharge regimes when compared with pasture land use, and modelling suggests that partial harvesting would moderate the magnitude of discharge variation compared with a full catchment plantation harvesting. The model efficiency coefficient (Nash–Sutcliffe model efficiency coefficient) varied from 0.665 to 0.799 for the total period of the study. Simulation of alternative harvesting scenarios suggested that at least 20% of the catchment planted area must be harvested to increase discharge. This model could be a useful practical tool in various plantation forestry contexts around the world. Copyright © 2016 John Wiley & Sons, Ltd.
Current knowledge of South American cladoceran diapause: A brief review
Authors: Iglesias Carlos , Bonecker Claudia , Brandão Luciana , Crispim Maria Cristina , Eskinazi‐Sant'Anna Eneida M. , Gerhard Miriam , Laço Portinho Jorge , Maia‐Barbosa Paulina , Panarelli Eliana , Santangelo Jayme M.
Published: August 2016

The study of the structure and dynamics of cladoceran egg banks in South America began only 15 years ago and the amount of knowledge, in addition to being scarce, is widely spread over partially national journals, theses, and books, and thus partially unavailable. We conducted a review of the literature published for this region, focusing mainly on the methodological approaches that have been applied and describe the main findings already published. The different methodological approaches make data comparability difficult. However, a total of 77 egg morphotypes were identified in the published studies. Among the variety of methods used, we suggest to adopt as the standard procedure: 1) pre isolation of eggs from the sediments by the “Sugar Flotation Method;” 2) identification, enumeration, and sorting of egg morphotypes present in the sample; 3) individual hatching of each egg morphotype; 4) adult individual identification to the species level according to available keys; and 5) linking identified eggs to identified species’ adults. The absence of identification keys constitutes a challenge. Therefore, collaborative research with the aim of generating pictorial taxonomical support for Neotropical resting eggs are encouraged. We believe the adoption of the suggested protocol might facilitate this issue. An extremely low hatching success was reported for most studies and the factors triggering the break of dormancy in the resting eggs coming from permanent systems remain unknown. In conclusion, resting egg studies are a novel and promising field in South America, but with many challenges that need to be addressed.
Baseline Cerebral Small Vessel Disease Is Not Associated with Gait Decline After Five Years
Authors: van der Holst Helena M. , van Uden Ingeborg W.M. , de Laat Karlijn F. , van Leijsen Esther M.C. , van Norden Anouk G.W. , Norris David G. , van Dijk Ewoud J. , Tuladhar Anil M. , de Leeuw Frank‐Erik
Published: August 2016

Background

Cerebral small vessel disease (SVD) is cross‐sectionally associated with gait disturbances, however, the relation between baseline SVD and gait decline over time is uncertain. Furthermore, diffusion tensor imaging (DTI) studies on gait decline are currently lacking.

Objective

To investigate the association between baseline imaging SVD markers and gait decline.

Methods

In 2006, 310 participants from the RUN DMC cohort, a prospective cohort with older adults aged 50–85 years with SVD, were included. Gait variables were assessed using a computerized walkway during baseline and follow‐up. Linear and logistic regression analyses were used to investigate the relation between imaging measures and gait decline and incident gait impairment (speed ≤ 1.0 m/s). Tract‐based spatial statistics (TBSS) was used to identify possible differences in DTI measures of white matter tracts between participants with and without incident gait impairment.

Results

Mean age was 63.3 years (SD: 8.4) and mean follow‐up duration 5.4 years (SD: 0.2). No significant associations between imaging measures and gait decline were found. TBSS analysis revealed no significant differences in DTI measures between participants with and without incident gait impairment after additional adjustment for SVD. In sub‐analyses, a high total WMH volume (OR: 2.8 for highest quartile, 95% CI: 1.1–7.1) and high infratentorial WMH volume (OR: 1.8 per SD increase, 95% CI: 1.1–2.9) were associated with an increased 5‐year risk of gait impairment, although this was not significant after correction for multiple testing.

Conclusion

Baseline imaging SVD markers were not associated with gait decline or incident gait impairment after 5 years. Future studies should investigate if SVD progression is related to gait deterioration.
Label‐free quantitative proteomic analysis of tolerance to drought in Pisum sativum
Authors: Castillejo María‐Ángeles , Iglesias‐García Rebeca , Wienkoop Stefanie , Rubiales Diego
Published: August 2016

Abiotic stresses caused by adverse environmental conditions are responsible for heavy economic losses on pea crop, being drought one of the most important abiotic constraints. Development of pea cultivars well adapted to dry conditions has been one of the major tasks in breeding programs. The increasing food requirements drive the necessity to broaden the molecular basis of tolerance to drought to develop pea cultivars well adapted to dry conditions. We have used a shotgun proteomic approach (nLC‐MSMS) to study the tolerance to drought in three pea genotypes that were selected based on differences in the level of water deficit tolerance. Multivariate statistical analysis of data unraveled 367 significant differences of 700 identified when genotypes and/or treatment were compared. More than half of the significantly changed proteins belong to primary metabolism and protein regulation categories. We propose different mechanisms to cope drought in the genotypes studied. Maintenance of the primary metabolism and protein protection seems a strategy for drought tolerance. On the other hand susceptibility might be related to maintenance of the homeostatic equilibrium, a very energy consuming process. Data are available via ProteomeXchange with identifier PXD004587.
Sliding threshold of spike‐rate dependent plasticity of a semiconducting polymer/electrolyte cell
Authors: Dong Wenshuai , Zeng Fei , Hu Yuandong , Chang Chiating , Li Xiaojun , Pan Feng , Li Guoqi
Published: August 2016

Spike‐rate dependent plasticity, one of the conventional learning protocols in neuroscience, has been achieved in semiconducting polymer/electrolyte cells. The frequency threshold θm of spike‐rate dependent plasticity is sliding in requirement of stability. In this work, various prior signal inputs are applied to poly[2‐methoxy‐5‐(2‐ethylhexyloxy)−1,4‐phenylenevinylene]/polyethylene oxide ‐Nd3+ cells to explore their effects on θm.The study find that a prior inhibitory input, i.e., a weak stimulation, moves θm in the low frequency direction, while a prior excitatory input, i.e., an intensive stimulation, moves θm in the high frequency direction. Our results demonstrate the adaptivity of ionic kinetics in macromolecules systems for signal handling and learning. We suggest that a sliding threshold is due to the variable active ionic domains depending on stimulation strength and history. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 2412–2417
Coupling of Plasma Chemistry, Vibrational Kinetics, Collisional‐Radiative Models and Electron Energy Distribution Function Under Non‐Equilibrium Conditions
Authors: Capitelli Mario , Colonna Gianpiero , D'Ammando Giuliano , Hassouni Khaled , Laricchiuta Annarita , Pietanza Lucia Daniela
Published: August 2016

The coupling between the electron energy distribution function (eedf) and the kinetics of vibrationally and electronically excited states is discussed. The first case study concerns the role of heterogeneous recombination in affecting the concentration of atomic hydrogen in RF plasmas, with consequences on eedf and negative ion formation. The coupling of eedf and a collisional‐radiative model for atomic hydrogen is discussed for optically thin and thick plasmas, finding large differences in the creation of eedf plateaux. The last case study deals with a self‐consistent coupling of eedf and kinetics of vibrationally and electronically excited states in CO2 cold plasmas emphasizing the role of pure vibrational mechanisms in the dissociation of CO2.
Calculation of Electron‐Scattering Cross Sections Relevant for Hypersonic Plasma Modeling
Authors: Laricchiuta Annarita , Celiberto Roberto , Capitelli Mario , Colonna Gianpiero
Published: August 2016

Electron‐impact induced, optically allowed excitations to the B 2Π and C 2Π states in NO molecule are considered in the framework of the similarity approach, accounting for the non‐adiabatic vibronic coupling perturbing the vibrational progression in the excited states. A model for the coupling is proposed from ab initio electronic structure calculations and theoretical oscillator strengths and Einstein coefficients are estimated for its validation. State‐to‐state and total cross sections are derived and, for the transition from the v″ = 0 level of the ground state, similarity results well compare with available experiments.
Effect of design specifications in dose‐finding trials for combination therapies in oncology
Authors: Hirakawa Akihiro , Sato Hiroyuki , Gosho Masahiko
Published: August 2016

Model‐based dose‐finding methods for a combination therapy involving two agents in phase I oncology trials typically include four design aspects namely, size of the patient cohort, three‐parameter dose‐toxicity model, choice of start‐up rule, and whether or not to include a restriction on dose‐level skipping. The effect of each design aspect on the operating characteristics of the dose‐finding method has not been adequately studied. However, some studies compared the performance of rival dose‐finding methods using design aspects outlined by the original studies. In this study, we featured the well‐known four design aspects and evaluated the impact of each independent effect on the operating characteristics of the dose‐finding method including these aspects. We performed simulation studies to examine the effect of these design aspects on the determination of the true maximum tolerated dose combinations as well as exposure to unacceptable toxic dose combinations. The results demonstrated that the selection rates of maximum tolerated dose combinations and UTDCs vary depending on the patient cohort size and restrictions on dose‐level skipping However, the three‐parameter dose‐toxicity models and start‐up rules did not affect these parameters. Copyright © 2016 John Wiley & Sons, Ltd.
Self‐aspiration sampling extractive electrospray ionization mass spectrometry (EESI‐MS) for high‐throughput analysis of liquid samples
Authors: Jia Bin , Zhang Shuai , Yan Ling , He Shoubo , Liu Baohong , Shen Huali , Yang Pengyuan
Published: August 2016

Rationale

Extractive electrospray ionization mass spectrometry (EESI‐MS) was invented as a typical ambient mass spectrometry method (AMS) and has been used for analyzing complex liquid samples. Here, we designed a Venturi effect‐based self‐aspiration sampling device and applied it to the EESI‐MS for high‐throughput analysis of liquid sample.

Methods

A special concentric nebulizer was designed and employed to produce a suction force for the direct aspiration of liquid samples, followed by ionization and detection. This sample aspiration process was explained and optimized using computational fluid dynamics (CFD) analysis. Experiment data were recorded to exhibit the sensitivity, memory effect, inter‐day reproducibility, throughput, and applicability of the self‐aspiration sampling EESI‐MS.

Results

The limit of detection (LOD) of this method was determined as 4.5 × 10−10 g/mL (S/N = 3) for caffeine, and the sample throughput and relative standard deviation (RSD) for full scan mode can reach 0.67 samples/s and 4.76%, respectively. Even for MS/MS mode, the frequency can still be kept at 0.4 samples/s (RSD = 4.71%). Inter‐day RSD examined in 1 week was below 10% for the signal of characteristic fragment ions of reserpine. Moreover, based on this method, the amount of caffeine in instant coffee was determined as 4.7%. This device was also proven to be suitable for the protein/peptide analysis.

Conclusions

These experiment results, especially the amazing results on sample throughput and inter‐day RSD, suggest that we provide a valuable device which can be used for the direct high‐throughput qualitative/quantitative mass spectrometry analysis of real liquid samples in ambient. Copyright © 2016 John Wiley & Sons, Ltd.