bluuebunny/crossref_metadata_2025 huggingface dataset:
A Practical Modular Course of Combinatorial and High‐Throughput Methods for Use in Academic Teaching Laboratories
Authors: Stöwe Klaus , Ausfelder Florian
Published: April 2013

Combinatorial and high‐throughput methods are increasingly common in industrial research. Academic institutions are often unable to afford the equipment necessary and to provide the maintenance required for permanent operation. Teaching is often more constrained by budget than by research topics. This article describes a modular course that has been designed to allow an affordable implementation of combinatorial and high‐throughput experiments in academic teaching laboratories. Currently, the course consists of five experimental modules and has already been successfully taught on two occasions.
Molecular Hydrogels with Esterase‐like Activity
Authors: Yang Chengbiao , Wang Huaimin , Li Dongxia , Wang Ling
Published: April 2013

The development of molecular hydrogels that can be applied for mimicking bioactive molecules attracts extensive interests of researchers in fields of self‐assembly. In this study, we reported on several molecular hydrogels based on naphthylacetic acid‐peptides containing L‐histidine formed by the heating‐cooling process. All hydrogels exhibited higher activity to hydrolyze 4‐nitrophenyl acetate (4‐NPA) than the free L‐histidine probably due the high density of L‐histidine residue at the surface of self‐assembled nanofibers. To calculate the 4‐NPA hydrolysis rates, the Michaelis‐Menten enzyme kinetics model was made. Among these gels, the gel of Nap‐GFFYGHY possesses the highest enzyme activity of making the ester bond cleavage, which is approximately 25 times higher than that of the control (free L‐histidine and Nap‐GFFYGYY). These results indicate that molecular hydrogels with self‐assembled nanofibers have great potential for the generation of self‐assembled multivalent materials.
Kba.62 and S100 protein expression in cytologic samples of metastatic malignant melanoma
Authors: Erdag Gulsun , Chowdhuri Sinchita Roy , Fetsch Patricia , Erickson Dana , Hughes Marybeth S. , Filie Armando C.
Published: April 2013

The diagnosis of melanoma can be challenging, especially in metastatic lesions, due to the ability of melanoma cells to morphologically mimic carcinoma, sarcoma and even lymphoma cells. Moreover, melanomas can exhibit negative immunostaining for the melanoma markers HMB‐45 and MART‐1/Melan‐A, often used in the diagnosis of this tumor. KBA.62 is a recently described antibody that reacts with benign and malignant melanocytic proliferations. In this study, we report our experience with KBA.62 and S100 protein immunostaining in the diagnosis of metastatic melanoma on fine‐needle aspiration and effusion samples. We reviewed 60 cytology samples from 58 patients with metastatic melanoma. Our results showed that KBA.62 stained 75% of the cases and S100 protein 87% of the cases. KBA.62 and S100 protein stained the majority of metastatic melanomas that were negative for HMB‐45 and MART‐1; KBA.62 stained 73% of the cases and S100 protein 73% of the cases. The majority (85%) of the cases negative for HMB‐45 and MART‐1 were positive for KBA.62 and/or S100 protein. Additionally, we also observed that KBA.62 staining was positive in the majority of epithelioid and spindle cell type melanoma cells. In conclusion, the performances of KBA.62 and S100 protein were similar and both markers are useful in the diagnosis of metastatic melanoma in cytology material, especially when the tumor cells lack expression of HMB‐45 and MART‐1. Diagn. Cytopathol. 2013;41:847‐851. © 2013 Wiley Periodicals, Inc.
Cytological diagnosis of metastatic glioblastoma in the pleural effusion of a lung transplant patient
Authors: Nauen David W. , Li Qing Kay
Published: April 2013

The extracranial metastasis of glioblastoma is a rare event. We report the case of a patient who developed metastatic glioblastoma in pleural effusion 15 months after lung transplant, with emphasis on differential diagnosis based on cytological material. In our case, tumor cells had pleomorphic nuclei, prominent nucleoli, and fine vesicular chromatin. Some were arranged in a poorly formed pseudo‐glandular architecture, mimicking a poorly differentiated adenocarcinoma. The cytological diagnosis of metastatic glioblastoma is difficult and depends critically on clinical history and suspicion, particularly in the transplant setting. Review of the literature indicates that transmission/metastasis of intracranial malignancy occurs rarely following organ transplantation, with some debate on the suitability for transplant of organs from affected donors. Although the situation is uncommon, this report of the cytological findings of extracranial glioblastoma may extend our current knowledge and provide additional differential diagnostic information for this entity. Diagn. Cytopathol. 2014;42:619–623. © 2013 Wiley Periodicals, Inc.
Preparation and analytical characterization of 1‐(1‐phenylcyclohexyl)piperidine (PCP) and 1‐(1‐phenylcyclohexyl)pyrrolidine (PCPy) analogues
Authors: Wallach Jason , Paoli Giorgia De , Adejare Adeboye , Brandt Simon D.
Published: April 2013

Classic examples of psychoactive arylcycloalkylamines include ketamine and 1‐(1‐phenylcyclohexyl)piperidine (PCP) and many others serve as important structural templates for neuropharmacological research. The recent emergence of PCP analogues that can be obtained from internet retailers requires the implementation of appropriate monitoring strategies for harm reduction purposes. Access to analytical data plays a key part when encountering these substances, especially if reference material is not available. The present study describes the synthesis of three substituted 1‐(1‐phenylcyclohexyl)piperidines, (3‐MeO‐, 4‐MeO‐ and 3‐Me‐PCP) and three substituted 1‐(1‐phenylcyclohexyl)pyrrolidine analogues (3‐MeO‐, 4‐MeO‐ and 3‐Me‐PCPy). Analytical characterizations of all six arylcyclohexylamines and their primary 1‐phenylcyclohexanamine intermediates included gas chromatography ion trap electron‐ and chemical ionization and high resolution mass spectrometry, liquid chromatography electrospray hybrid triple‐quadrupole linear ion trap tandem mass spectrometry, infrared, diode array detection and 1H and 13C nuclear magnetic resonance (NMR) spectroscopy. Solvent (CDCl3 vs. d6‐DMSO) and protonation effects (free bases vs hydrochloride salts) were studied in order to investigate the impact on shifts and splitting patterns, for example, when attempting to assign separate axial and equatorial proton chemical shifts of NMR spectra. Differentiation between the isomeric 3‐MeO‐/4‐MeO‐PCP and PCPy analogues was feasible under mass spectral conditions. Gas chromatography analysis appeared to induce notable degradation of the 4‐MeO‐substituted analytes, especially when dealing with the HCl salts which led to the detection of the substituted 1‐phenylcyclohex‐1‐ene nucleus. This phenomenon was observed to be less pronounced with the 3‐MeO isomers, possibly due to the resonance properties of the para‐methoxy group followed by more facile elimination of the amine. Copyright © 2013 John Wiley & Sons, Ltd.
Interpretations arising from Wrightian and Malthusian fitness under strong frequency dependent selection
Authors: Wu Bin , Gokhale Chaitanya S. , van Veelen Matthijs , Wang Long , Traulsen Arne
Published: April 2013

Fitness is the central concept in evolutionary theory. It measures a phenotype's ability to survive and reproduce. There are different ways to represent this measure: Malthusian fitness and Wrightian fitness. One can go back and forth between the two, but when we characterize model properties or interpret data, it can be important to distinguish between them. Here, we discuss a recent experiment to show how the interpretation changes if an alternative definition is used.
Food stoichiometry affects the outcome of Daphnia–parasite interaction
Authors: Aalto Sanni L. , Pulkkinen Katja
Published: April 2013

Phosphorus (P) is an essential nutrient for growth in consumers. P‐limitation and parasite infection comprise one of the most common stressor pairs consumers confront in nature. We conducted a life‐table study using a Daphnia–microsporidian parasite model, feeding uninfected or infected Daphnia with either P‐sufficient or P‐limited algae, and assessed the impact of the two stressors on life‐history traits of the host. Both infection and P‐limitation negatively affected some life‐history traits tested. However, under P‐limitation, infected animals had higher juvenile growth rate as compared with uninfected animals. All P‐limited individuals died before maturation, regardless of infection. The numbers of spore clusters of the microsporidian parasite did not differ in P‐limited or P‐sufficient hosts. P‐limitation, but not infection, decreased body phosphorus content and ingestion rates of Daphnia tested in separate experiments. As parasite spore production did not suffer even under extreme P‐limitation, our results suggest that parasite was less limited by P than the host. We discuss possible interpretations concerning the stoichiometrical demands of parasite and suggest that our results are explained by parasite‐driven changes in carbon (C) allocation of the hosts. We conclude that the impact of nutrient starvation and parasite infection on consumers depends not only on the stoichiometric demands of host but also those of the parasite.
Ring‐Opening Reactions of Cyclopropenedicarboxylates with Organolithiums and Organozincs
Authors: Liu Yu , Yu Qiong , Ma Shengming
Published: April 2013

Ring‐opening reactions of cyclopropenedicarboxylates with organolithiums and organozincs have been studied. Organolithiums and dialkyl‐ or diphenylzincs afforded a series of 1‐alkenyl malonates with attack occurring by the organic group from the organometallic reagent at the less substituted sp2‐hybridized carbon of the cyclopropene moiety. Mechanistic studies proved both anion and dianion intermediates are involved in the reactions with organolithiums. Phenylcyclopropenedicarboxylate and phenylzinc bromide underwent a ring‐opening dimerization to afford a 1,4‐enyne product.
Foldameric β‐H18/20P Mixed Helix Stabilized by Head‐to‐Tail Contacts: A Way to Higher‐Order Structures
Authors: Szolnoki Éva , Hetényi Anasztázia , Mándity István M. , Fülöp Ferenc , Martinek Tamás A.
Published: April 2013

Peptidic foldamers are known to exhibit increased diversity in the periodic secondary‐structure space in comparison with their natural counterparts, but their higher‐order self‐organization has been studied less thoroughly. In theory, large‐diameter peptide foldamer helices have the capability of self‐recognition through axial helix–helix interactions (e.g., head‐to‐tail), but this phenomenon has previously been observed in only one instance. In this article we report on the discovery of the largest‐diameter β‐peptidic mixed helix to date, the H18/20P helix. Its formation is solvent‐dependent and its folding occurs cooperatively through head‐to‐tail self‐assembly in solution. These findings suggest that axial helix–helix interactions can serve as a new mode for the formation of tertiary/quaternary structures for peptide foldamers, which also show higher‐order structural diversity than natural proteins.
A Convenient Route to 1‐Alkyl‐5‐trifluoromethyl‐1,2,3‐triazole‐4‐carboxylic Acids Employing a Diazo Transfer Reaction
Authors: Iminov Rustam T. , Mashkov Alexander V. , Chalyk Bohdan A. , Mykhailiuk Pavel K. , Tverdokhlebov Anton V. , Tolmachev Andrey A. , Volovenko Yulian M. , Shishkin Oleg V. , Shishkina Svetlana V.
Published: April 2013

The reaction of ethyl 3‐(alkylamino)‐4,4,4‐trifluoro‐but‐2‐enoates with mesyl azide in the presence of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU) gave ethyl 1‐alkyl‐5‐trifluoromethyl‐1,2,3‐triazole‐4‐carboxylates in good yields. Further hydrolysis of the ester group afforded the title compounds on a multigram scale.
Dinuclear Chloride‐Binding Foldamers Based on Fluorescent Oligoureas
Authors: Yang Peiju , Wang Jiamin , Jia Chuandong , Yang Xiao‐Juan , Wu Biao
Published: April 2013

A series of dinuclear chloride‐binding foldamers – (TEA)2[L1Cl2]·Et2O (1), (TEA)2[L2Cl2] (2), (TBA)2[L3Cl2] (3), (TBA)2[L4Cl2] (4), [K(18‐crown‐6)]2[L4Cl2]·H2O (5), and (TBA)2[L5Cl2]·H2O (6) – have been synthesized from naphthyl‐ and anthracenyl‐decorated oligoureas (tetrakisurea to hexakisurea, L1–L5). In the crystal structures of 1–6, the oligoureas adopt helical conformations and two chloride anions are bound inside by the urea groups. The solution binding properties of L1–L5 toward chloride ion were investigated by 1H NMR and fluorescence spectroscopy. Upon binding of the anions, characteristic downfield shifts of the NH signals and enhanced fluorescent emission relative to the free ligands were observed. In DMSO solution, the ligands each display a 1:1 binding ratio to chloride, with association constants of K = 1.16–7.58 × 102 M–1, which contrasts with the 1:2 (host to guest) binding mode in the crystal structures. However, the formation of dinuclear foldamers in the less polar solvent CHCl3 was indicated by the HRMS (ESI) spectra.
The Influence of Boronate Groups on the Selectivity of the Br–Li Exchange in Model Dibromoaryl Boronates
Authors: Durka Krzysztof , Luliński Sergiusz , Smętek Jaromir , Dąbrowski Marek , Serwatowski Janusz , Woźniak Krzysztof
Published: April 2013

The selectivity of the Br/Li exchange reaction of 6‐butyl‐2‐(2,5‐dibromophenyl)‐1,3,6,2‐dioxazaborocane (2,5‐Br2C6H3B(OCH2CH2)2NBu) and the analogous anionic derivatives, 2,5‐Br2C6H3B(OiPr)3Li and 2,5‐Br2C6H3BF3K, was investigated using nBuLi as the lithiating reagent. In the case of the former compound there was a slight preference for lithiation at the 5‐position. For 2,5‐Br2C6H3B(OiPr)3Li, the lithiation occured exclusively at C5, but for 2,5‐Br2C6H3BF3K, 2‐lithiation was preferred. Calculations performed for the lithiation of ortho‐ and meta‐brominated phenyl boronates revealed that ortho‐lithiated aryl boronates are thermodynamically more stable, but that the Br/Li exchange is generally dictated by kinetics, which accounts for the variation of selectivity depending on the type of boronate group. In addition, the successful generation of the 2,5‐dilithiophenyl boronate species 2,5‐Li2C6H3B(OCH2CH2)2NBu by a double Br/Li interconversion is reported. The Br/Li exchange in the related 6‐butyl‐2‐[3‐(2,5‐dibromothienyl)]‐1,3,6,2‐dioxazaborocane, 2,5‐Br2‐3‐ThB(OCH2CH2)2NBu, occured preferentially at the 5‐position, but the product was readily transformed into the more stable 2‐lithiated isomer. The use of 2 equiv. of nBuLi resulted in the efficient formation of the dilithiated species, 2,5‐Li2‐3‐ThB(OCH2CH2)2NBu. The obtained lithiated aryl boronates were converted into functionalized arylboronic acids by treatment with selected electrophiles.
Pretreatment of raw glycerol with activated carbon for 1,3‐propanediol production by Clostridium butyricum
Authors: Zhu Chunjie , Chen Bin , Fang Baishan
Published: April 2013

Raw glycerol contains inhibiting impurities that render its bioconversion difficult. In this work, raw glycerol used in 1,3‐propanediol fermentation by Clostridium butyricum was pretreated with activated carbon. Compared with pure glycerol, the untreated raw glycerol inhibited fermentation. Therefore, the raw glycerol was treated using dusty activated carbon as an adsorbent in batch fermentation, resulting in a shortening of the fermentation time from 18.5 to 13.3 h. The effects of pH, dusty activated carbon amount, and adsorption time on the pretreatment results were investigated using uniform design. The pH had a much lower impact and the optimal pretreatment conditions were achieved: pH 3.0, 0.5 g dusty activated carbon/150 g raw glycerol, adsorption time 3 h. Batch cultures on pretreated raw glycerol were comparable to those on pure glycerol. The 1,3‐propanediol concentration in fed‐batch cultivation was 49.3 g/L on pretreated raw glycerol while it was 40.8 g/L on untreated raw glycerol. The FTIR spectra of dusty activated carbon before and after adsorption indicated that the inhibiting impurities were probably aromatic compounds. This work indicates that pretreatment is necessary to ferment raw glycerol to 1,3‐propanediol and that pretreatment with dusty activated carbon is an efficient, economical, and simple method.
Stress tensor changes related to fluid injection at The Geysers geothermal field, California
Authors: Martínez‐Garzón Patricia , Bohnhoff Marco , Kwiatek Grzegorz , Dresen Georg
Published: April 2013

Studying variations of the stress field in reservoirs caused by massive fluid injection is important toward an improved understanding of geomechanical processes involved. We report on spatio‐temporal variations of the local stress tensor orientation at The Geysers geothermal field, California. We apply two stress inversion methods with detailed uncertainty assessments using a selection of events recorded between 2007 and 2012. Our results clearly indicate variations in the orientation of the principal stress axes for the reservoir as a whole showing a normal faulting regime at the reservoir depth between 2 and 3.7 km bounded by a strike‐slip regime above and below. Analyzing the temporal evolution of the stress tensor orientation for a prominent seismicity cluster we observe a clear correlation of changes in orientation for σ1–3 with the highest injection rates. These results suggest that temporal changes in the stress tensor orientation could contribute to characterize reservoirs during stimulation.
Nutrient enrichment of the subarctic Pacific Ocean pycnocline
Authors: Whitney Frank A. , Bograd Steven J. , Ono Tsuneo
Published: April 2013

At the end of the global thermohaline circulation, the subarctic Pacific is the richest nutrient repository in the world oceans. Trends towards lower oxygen and higher nutrients in waters below the surface layer (the pycnocline) have been observed in recent decades. We assess these trends using data from four programs and suggest the enrichment of pycnocline nitrate (200 Gmol y−1) is essential in keeping supply to the surface ocean constant, despite increasing upper ocean stratification. A nitrate budget helps identify possible vertical processes that could account for nutrient redistribution. We hypothesize that warming and oxygen loss in the deeper pycnocline, arising from ice loss in the Okhotsk Sea, have initiated a largely vertical redistribution of nutrients due to compression of vertical migrator habitat and/or changes in dissolution of sinking particulates. Coupled climate‐ecosystem models will need to incorporate these processes to more fully understand projected changes in the subarctic Pacific.
Natural aerosol direct and indirect radiative effects
Authors: Rap Alexandru , Scott Catherine E. , Spracklen Dominick V. , Bellouin Nicolas , Forster Piers M. , Carslaw Kenneth S. , Schmidt Anja , Mann Graham
Published: April 2013

Natural aerosol plays a significant role in the Earth's system due to its ability to alter the radiative balance of the Earth. Here we use a global aerosol microphysics model together with a radiative transfer model to estimate radiative effects for five natural aerosol sources in the present‐day atmosphere: dimethyl sulfide (DMS), sea‐salt, volcanoes, monoterpenes, and wildfires. We calculate large annual global mean aerosol direct and cloud albedo effects especially for DMS‐derived sulfate (–0.23 Wm–2 and –0.76 Wm–2, respectively), volcanic sulfate (–0.21 Wm–2 and –0.61 Wm–2) and sea‐salt (–0.44 Wm–2 and –0.04 Wm–2). The cloud albedo effect responds nonlinearly to changes in emission source strengths. The natural sources have both markedly different radiative efficiencies and indirect/direct radiative effect ratios. Aerosol sources that contribute a large number of small particles (DMS‐derived and volcanic sulfate) are highly effective at influencing cloud albedo per unit of aerosol mass burden.
Web Tools for Predicting Metal Binding Sites in Proteins
Authors: Sobolev Vladimir , Edelman Marvin
Published: April 2013

Approximately one third of proteins bind metal ions for stability and/or enzymatic function. However, on a structural level, only a small fraction of binding sites have been resolved. Metal binding site predictions can serve as a first step in putative function assignment for many unannotated proteins. Sequence based and structure based methods for metal binding site predictions are reviewed here. The CHED and SeqCHED methods of prediction from apo protein structures and translated gene sequences, respectively, are described in detail, including their web server applications. The relevance of SeqCHED to the analysis of single nucleotide polymorphisms (SNPs) associated with disease related metal binding sites is illustrated.
MODELLING OF AN IRRIGATION SCHEME WITH SEDIMENT‐LADEN WATER FOR IMPROVED WATER MANAGEMENT: A CASE STUDY OF SUNSARI MORANG IRRIGATION SCHEME, NEPAL
Authors: Paudel Krishna P. , Schultz Bart , Depeweg Herman
Published: April 2013

Irrigation schemes with sediment‐laden water are generally performing significantly below expectation and potential. Managing such irrigation schemes is challenging as in most cases the management aspects of sediment transport were not included in the design process and in some cases the proposed management plans are difficult to follow. The sediment transport process is affected by the flow conditions in the canal, and the latter are affected by the canal operation modes. Hence, system management is one of the important aspects that influence the sediment transport process. The mathematical model SETRIC has been used to analyse the existing management mode and its effect on the sediment transport process of the Sunsari Morang Irrigation Scheme in Nepal. Evaluation showed that the sub‐secondary canals of the Secondary Canal S9 have different sediment transport capacities. Some canals are facing more deposition problems than others. The problem is further increased by the existing water delivery mode. The modelling results show that it is possible to reduce sedimentation problems by improving existing water management practices. The proposed water management plan, based on the existing infrastructure, could be implemented to address the sediment transport problems in this scheme and other schemes with appropriate adaptation. Copyright © 2013 John Wiley & Sons, Ltd.
Preparation of polycaprolactone microspheres‐aggregated scaffold with ultra big pores and fuzzy sphere surface by a one‐step phase separation method
Authors: Wang Meicong , Ma Lie , Li Dan , Jiang Pengfei , Gao Changyou
Published: April 2013

A microspheres‐aggregated scaffold with ultra big pores (over 300 μm) and fuzzy microspheres is fabricated by incubating polycaprolactone (PCL)/tetrahydrofuran (THF) solution in a −20°C refrigerator, following by freeze‐drying. Formation of the scaffold is mainly governed by the crystallization of the PCL polymer at appropriate conditions. All the 10–20% PCL/THF solutions yield the microspheres‐aggregated scaffolds when the initial solution temperature is higher than 37°C, whereas the 10–15% solutions form dense membranes when the initial solution temperature is below 25°C. The size of the microspheres and pores is as large as 70–150 μm and 170–816 μm, respectively. The PCL microspheres‐aggregated scaffold can better support the adhesion and proliferation of bone marrow mesenchymal stem cells (BMSCs) compared to the traditional porous scaffold obtained by a porogen leaching method. The tendencies of chondrogenesis and osteogenesis differentiation of BMSCs are observed on the microspheres‐aggregated scaffold and the ordinary porous scaffold, respectively. © 2013 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 101A: 3219‐3227, 2013.
Comparative Cytotoxicity, Oxidative Stress, and Cytokine Secretion Induced by Two Cyanotoxin Variants, Microcystin LR and RR, in Human Intestinal Caco‐2 Cells
Authors: Huguet Antoine , Henri Jérôme , Petitpas Mélanie , Hogeveen Kevin , Fessard Valérie
Published: April 2013

While MC‐LR and MC‐RR share significant structural similarity, MC‐RR is less cytotoxic than MC‐LR. In the current study, we have compared the effects of MC‐LR and MC‐RR in Caco‐2 cells by evaluating cytotoxicity, oxidative stress (reactive oxygen species production), and the cellular proinflammatory response (IL‐6 and IL‐8 production). Following treatment with 100 µM microcystins (MC), cytotoxicity was two‐fold greater with MC‐LR as compared to MC‐RR after 24 h exposure. Whereas the reactive oxygen species production and IL‐6 secretion were similar following a 24‐h treatment with either MC, 100 µM MC‐LR induced a five‐fold greater IL‐8 secretion when compared to MC‐RR. Our study has demonstrated that, although both MC‐LR and MC‐RR induced some cytotoxicity in human intestinal cells, a major difference in IL‐8 production was observed between the two variants. © 2013 Wiley Periodicals, Inc. J BiochemMol Toxicol 27:253‐258, 2013; View this article online at wileyonlinelibrary.com. DOI 10.1002/jbt.21482
Neuroprotective Effects of Erythropoietin in Patients with Carbon Monoxide Poisoning
Authors: Pang Li , Bian Miao , Zang Xiu‐Xian , Wu Yang , Xu Da‐Hai , Dong Ning , Wang Zhi‐Hao , Yan Bai‐Ling , Wang Da‐Wei , Zhao Hui‐Jie , Zhang Nan
Published: April 2013

The purpose of this study was to evaluate the efficacy of erythropoietin (EPO) for treating patients with carbon monoxide (CO) poisoning. We conducted a randomized, prospective study of 103 patients with CO poisoning in two groups: an EPO group (n = 54; patients received EPO) and a placebo group (n = 49; patients received normal saline). The study endpoints were the functional outcome at day 30 (the Barthel index and neurologic sequelae), National Institutes of Health Stroke Scale (NIHSS) score, and the levels of S‐100β. At 18 days, the NIHSS score improved significantly and S‐100β levels significantly decreased in patients in the EPO group. At 30 days, patients in the EPO group had a superior Barthel index and fewer patients had delayed neurologic sequelae (DNS). This study demonstrated that early administration of EPO to patients with CO poisoning improved neurological outcomes and reduced the incidence of DNS. © 2013 Wiley Periodicals, Inc. J BiochemMol Toxicol 27:266‐271, 2013; View this article online at wileyonlinelibrary.com. DOI 10.1002/jbt.21484
Photodeactivation paths in norbornadiene
Authors: Antol Ivana
Published: April 2013

The first high level ab initio quantum‐chemical calculations of potential energy surfaces (PESs) for low‐lying singlet excited states of norbornadiene in the gas phase are presented. The optimization of the stationary points (minima and conical intersections) and the recalculation of the energies were performed using the multireference configuration interaction with singles (MR‐CIS) and the multiconfigurational second‐order perturbation (CASPT2) methods, respectively. It was shown that the crossing between valence V2 and Rydberg R1 states close to the Franck–Condon (FC) point permits an easy population switch between these states. Also, a new deactivation path in which the doubly excited state with (π3)2 configuration (DE) has a prominent role in photodeactivation from the R1 state due to the R1/DE and the DE/V1 conical intersections very close to the R1 and DE minima, respectively, was proposed. Subsequent deactivation from the V1 to the ground state goes through an Olivucci–Robb‐type conical intersection that adopts a rhombic distorted geometry. The deactivation path has negligible barriers, thereby making ultrafast radiationless decay to the ground state possible. © 2013 Wiley Periodicals, Inc.
On the vibrational linear and nonlinear optical properties of compounds involving noble gas atoms: HXeOXeH, HXeOXeF, and FXeOXeF
Authors: Avramopoulos Aggelos , Reis Heribert , Luis Josep M. , Papadopoulos Manthos G.
Published: April 2013

The vibrational (hyper)polarizabilities of some selected Xe derivatives are studied in the context of Bishop–Kirtman perturbation theory (BKPT) and numerical finite field methodology. It was found that for this set of rare gas compounds, the static vibrational properties are quite large, in comparison to the corresponding electronic ones, especially those of the second hyperpolarizability. This also holds for the dc‐Pockels β(−ω;ω,0), Kerr γ(−ω;ω,0,0) and electric field second harmonic generation γ (−2ω;ω,ω,0) effects, although the computed nuclear relaxation (nr) vibrational contributions are smaller in magnitude than the static ones. HXeOXeH was used to study the effects of electron correlation, basis set, and geometry. Geometry effects were found to lead to noticeable changes of the vibrational and electronic second hyperpolarizability. A limited study of the effect of Xe insertion to the nr vibrational properties is also reported. Assessment of the results revealed that Xe insertion has a remarkable effect on the nr (hyper)polarizabilities. In terms of the BKPT, this is associated with a remarkable increase of the electrical and mechanical anharmonicity terms. The latter is consistent with the anharmonic character of several vibrational modes reported for rare gas compounds. © 2013 Wiley Periodicals, Inc.
Pipek–Mezey localization of occupied and virtual orbitals
Authors: H⊘yvik Ida‐Marie , Jansik Branislav , J⊘rgensen Poul
Published: April 2013

Recent advances in orbital localization algorithms are used to minimize the Pipek–Mezey localization function for both occupied and virtual Hartree–Fock orbitals. Virtual Pipek–Mezey orbitals for large molecular systems have previously not been considered in the literature. For this work, the Pipek–Mezey (PM) localization function is implemented for both the Mulliken and a Löwdin population analysis. The results show that the standard PM localization function (using either Mulliken or Löwdin population analyses) may yield local occupied orbitals, although for some systems the occupied orbitals are only semilocal as compared to state‐of‐the‐art localized occupied orbitals. For the virtual orbitals, a Löwdin population analysis shows improvement in locality compared to a Mulliken population analysis, but for both Mulliken and Löwdin population analyses, the virtual orbitals are seen to be considerably less local compared to state‐of‐the‐art localized orbitals. © 2013 Wiley Periodicals, Inc.
Spectroscopic characterization of graphene films grown on Pt(111) surface by chemical vapor deposition of ethylene
Authors: Cazzanelli Enzo , Caruso T. , Castriota M. , Marino A. R. , Politano A. , Chiarello G. , Giarola M. , Mariotto G.
Published: April 2013

This work reports the peculiar properties of a graphene film prepared by the chemical vapor deposition of ethylene in high vacuum on a well oriented and carefully cleaned Pt(111) crystal surface maintained at high temperature. In‐situ and ex‐situ characterization techniques (low‐energy electron diffraction, high‐resolution electron energy loss spectroscopy, scanning electron microscopy and Raman micro‐spectroscopy) used here indicate the prevalence of single‐layer regions and the presence of two different orientations of the graphene sheets with respect to the Pt(111) substrate. In most of the deposited area, evidence is found of a compressive stress for the graphene lattice, as a net result of the growth process on a metal substrate. This graphene film grown on Pt(111) exhibits a lower degree of order and of homogeneity with respect to the exfoliated graphene on Si/SiO2, as it is found generally for graphene on metals, but several characterization techniques indicate a better quality than in previous deposition experiments on the same metal substrate. Copyright © 2013 John Wiley & Sons, Ltd.
Characteristic Raman lines of phenylalanine analyzed by a multiconformational approach
Authors: Hernández Belén , Pflüger Fernando , Kruglik Sergei G. , Ghomi Mahmoud
Published: April 2013

Thanks to a considerable modulation of electronic polarizability, six phenylalanine (Phe) vibration modes located at ca. 1606, 1586, 1207, 1031, 1004 and 622 cm−1 appear as intense or medium bands in the Raman spectra of peptides and proteins, as confirmed by the Raman data collected from free amino acid, somatostatin and bovine serum albumin (BSA). To get information on the nature and location of these lines, we resorted to a multiconformational analysis which consists in a systematic investigation of the structural and vibrational features of hydrated Phe in a conformational space depending on four angular variables: φ, ψ, χ1 and χ2. The first two variables correspond to the Phe backbone torsion angles, whereas the latter two refer to its side chain. Based on a protocol described in an accompanying report on glycine and its protonated and deprotonated species, we have prepared an initial set of 123 initial clusters of Phe + 5H2O, including all plausible values of the above mentioned conformational angles. The results of their geometry optimization, by means of the density functional theory using the B3LYP hybrid functional, were first analyzed through the comparison between the E(χ1, χ2) energy maps obtained either by an explicit or by an implicit hydration model. Then, a set of nine doubly minimized clusters corresponding to the deepest local minima were used for further structural and vibrational analysis. Beyond providing a reliable assignment for the above mentioned characteristic Raman lines, the theoretical spectrum allowed us to carry out an overview of the whole observed data of Phe in aqueous solution. Copyright © 2013 John Wiley & Sons, Ltd.
Bilateral pallidal stimulation for Wilson's disease
Authors: Sidiropoulos Christos , Hutchison William , Mestre Tiago , Moro Elena , Prescott Ian A. , Mizrachi Alejandro Valencia , Fallis Melanie , Rughani Anand I. , Kalia Suneil K. , Lozano Andres , Fox Susan
Published: April 2013

Background

To report on the clinical efficacy of bilateral globus pallidus internus deep brain stimulation in a 29‐year‐old patient with severe generalized dystonia secondary to Wilson's disease.

Methods

The primary outcome measure was the Burke‐Fahn‐Marsden Dystonia Scale motor severity score (blinded assessment) and the secondary outcome measures were the Abnormal Involuntary Movement Scale (blinded assessment) and the Zaritt Caregiver Burden Interview score, at 20‐week postoperative follow up.

Results

There was a 14% improvement in the Burke‐Fahn‐Marsden Dystonia Scale motor severity score. Abnormal Involuntary Movement Scale score remained unchanged while the Zaritt Caregiver Burden Interview score improved by 44.4%.

Conclusions

Bilateral globus pallidus deep brain stimulation can be effective in ameliorating dystonia and caregiver burden in Wilson's disease. Outcomes may depend on the stage of the disease at which the surgical procedure is completed. © 2013 Movement Disorder Society
Adiabatic multi‐echo 31P spectroscopic imaging (AMESING) at 7 T for the measurement of transverse relaxation times and regaining of sensitivity in tissues with short T2* values
Authors: van der Kemp W. J. M. , Boer V. O. , Luijten P. R. , Stehouwer B. L. , Veldhuis W. B. , Klomp D. W. J.
Published: April 2013

An adiabatic multi‐echo spectroscopic imaging (AMESING) sequence, used for 31P MRSI, with spherical k‐space sampling and compensated phase‐encoding gradients, was implemented on a whole‐body 7‐T MR system. One free induction decay (FID) and up to five symmetric echoes can be acquired with this sequence. In tissues with low T2* and high T2, this can theoretically lead to a potential maximum signal‐to‐noise ratio (SNR) increase of almost a factor of three, compared with a conventional FID acquisition with Ernst‐angle excitation. However, with T2 values being, in practice, ≤400 ms, a maximum enhancement of approximately two compared with low flip Ernst‐angle excitation should be feasible. The multi‐echo sequence enables the determination of localized T2 values, and was validated with 31P three‐dimensional MRSI on the calf muscle and breast of a healthy volunteer, and subsequently applied in a patient with breast cancer. The T2 values of phosphocreatine, phosphodiesters (PDE) and inorganic phosphate in calf muscle were 193 ± 5 ms, 375 ± 44 ms and 96 ± 10 ms, respectively, and the apparent T2 value of γ‐ATP was 25 ± 6 ms. A T2 value of 136 ± 15 ms for inorganic phosphate was measured in glandular breast tissue of a healthy volunteer. The T2 values of phosphomonoesters (PME) and PDE in breast cancer tissue (ductulolobular carcinoma) ranged between 170 and 210 ms, and the PME to PDE ratios were calculated to be phosphoethanolamine/glycerophosphoethanolamine = 2.7, phosphocholine/glycerophosphocholine = 1.8 and PME/PDE = 2.3. Considering the relatively short T2* values of the metabolites in breast tissue at 7 T, the echo spacing can be short without compromising spectral resolution, whilst maximizing the sensitivity. Copyright © 2013 John Wiley & Sons, Ltd.
A series of 238 cytomegalovirus primary infections during pregnancy: description and outcome
Authors: Picone O. , Vauloup‐Fellous C. , Cordier A. G. , Guitton S. , Senat M. V. , Fuchs F. , Ayoubi J. M. , Grangeot Keros L. , Benachi A.
Published: April 2013

Objective

To analyze the outcome of maternal primary cytomegalovirus (CMV) infection.

Methods

Retrospective analysis of a cohort of 238 patients with maternal primary CMV infection detected at routine screening. The cases were managed with serial ultrasound (US) scans, and amniocentesis was performed in 36.1% of cases. All prenatal results were confirmed at birth.

Results

The average age was 31.9 (18–44) years. Patients were symptomatic in 21% of cases. The rate of intrauterine transmission was 24.9%, and it was 8.8%, 19%, 30.6%, 34.1% and 40% in the preconceptional period, the periconceptional period, and the first, second and third trimesters of pregnancy, respectively (p = 0.025). There was a significantly higher risk of US abnormalities when maternal infection occurred during the preconceptional or periconceptional period and the first trimester compared with later (p < 0.001). Because of US abnormalities, pregnancy was terminated in 18 cases at the parents' request. Three infected newborns were symptomatic; all three cases were suspected at US before birth. We did not observe any symptomatic fetal infection when maternal infection occurred after 14 weeks of gestation. A number of clinically asymptomatic cases (5.5%) developed hearing loss.

Conclusion

The rate of materno fetal transmission is linearly correlated to the gestational age at infection. No severe case of congenital infection was observed if maternal infection occurred after 14 weeks of gestation. © 2013 John Wiley & Sons, Ltd.
Gestational age and maternal weight effects on fetal cell‐free DNA in maternal plasma
Authors: Wang Eric , Batey Annette , Struble Craig , Musci Thomas , Song Ken , Oliphant Arnold
Published: April 2013

Objective

To determine the effects of gestational age and maternal weight on percent fetal cell‐free DNA (cfDNA) in maternal plasma and the change in fetal cfDNA amounts within the same patient over time.

Methods

The cfDNA was extracted from maternal plasma from 22 384 singleton pregnancies of at least 10 weeks gestation undergoing the HarmonyTM Prenatal Test. The Harmony Prenatal Test determined fetal percentage via directed analysis of cfDNA.

Results

At 10 weeks 0 days to 10 weeks 6 days gestation, the median percent fetal cfDNA was 10.2%. Between 10 and 21 weeks gestation, percent fetal increased 0.1% per week (p < 0.0001), and 2% of pregnancies were below 4% fetal cfDNA. Beyond 21 weeks gestation, fetal cfDNA increased 1% per week (p < 0.0001). Fetal cfDNA percentage was proportional to gestational age and inversely proportional to maternal weight (p = 0.0016). Of 135 samples that were redrawn because of insufficient fetal cfDNA of the initial sample, 76 (56%) had greater than 4% fetal cfDNA in the sample from the second draw.

Conclusion

Fetal cfDNA increases with gestation, decreases with increasing maternal weight, and generally improves upon a blood redraw when the first attempt has insufficient fetal cfDNA. © 2013 John Wiley & Sons, Ltd.
Living with Diabetes: an educational model of care for new onset diabetes
Authors: Shaban Clare , Jenkins Emma , Knott Julia , Ryder Jacqueline , Cavan David
Published: April 2013

The first year following diagnosis is a critical time for those newly diagnosed with type 1 diabetes and is likely to influence long‐term glycaemic control.

This paper describes a group education programme, Living with Diabetes (LwD), and reports the outcome data at one year and three years after diagnosis. HbA1c was compared with outcomes from the cohort diagnosed during the four years prior to the inception of LwD.

We have demonstrated that, in terms of HbA1c, the programme achieved outcomes similar to the traditional model with similar staff resources. The LwD pathway required an additional 2.9 hours per patient but HbA1c values were consistently lower in those who attended all sessions.

The data suggest the need for more concerted attention to engage patients in an ongoing care pathway during the early years following diagnosis. An evaluation of the programme suggested that patients valued the relaxed non‐hierarchical nature of the group and the opportunity to share with and ask questions of their peers. Copyright © 2013 John Wiley & Sons.
Introducing a diabetes e‐learning module: a means of improving junior doctors' confidence and ability in managing inpatients with diabetes
Authors: Al‐Yassin A , Al‐Khaja A , Jichi F , Clarke C , Lisk C , Katz JR
Published: April 2013

The aims of this study were to determine whether the introduction of a diabetes management e‐module can increase junior doctors' confidence in managing inpatients with diabetes and contribute to improvements in patient care.

A diabetes e‐module was introduced at Barnet and Chase Farm Hospitals NHS Trust in October 2010. Junior doctors completed it and undertook an online exam at the end. Junior doctors were surveyed once, six to eight months after completing the e‐module, and retrospectively ranked their confidence and knowledge levels in managing inpatients with diabetes before and after completing the e‐module. Patient care was assessed by comparing the National Diabetes Inpatient Audit (NaDIA) findings at Barnet Hospital before and at two time points after the introduction of the e‐module.

After undertaking the e‐module there were statistically significant increases in the self‐ranked confidence and knowledge levels of junior doctors regarding diabetes management. This included improvements in identifying different types of insulin, making insulin dose adjustments for hypoglycaemia/hyperglycaemia and a reduction in reported prescription errors. The results from the NaDIA also suggest an improvement in ‘good diabetes days’ for insulin‐treated patients with diabetes and a pattern of reduction in prescription and management errors.

This study demonstrates that an inpatient diabetes management e‐module increases junior doctors' knowledge and confidence in managing diabetes. A multi‐centre study would be needed to confirm whether this translates into better management of inpatients with diabetes. E‐modules may be used to cover further topics in diabetes, and to support nursing and patient education. Copyright © 2013 John Wiley & Sons. Practical Diabetes 2013; 30(3): 122–127
Electrochemical synthesis of poly(indole‐co‐thiophene) on low‐nickel stainless steel and its anticorrosive performance in 0.5 mol L−1H2SO4
Authors: Gopi Dhanaraj , Saraswathy Ramanathan , Kavitha Louis , Kim Dae‐Kyeong
Published: April 2013

The electrochemical synthesis of poly(indole‐co‐thiophene) copolymer coatings was achieved on low‐nickel stainless steel (LN SS) with the cyclic voltammetry technique using indole and thiophene monomers in acetonitrile medium containing lithium perchlorate. The optimization of synthesis parameters such as monomer feed ratio and various scan rates was studied and also their influence on the morphology of the copolymer coatings on LN SS. For the first time, a possible radical cationic electro‐copolymerization mechanism is also proposed in order to understand the electrochemical synthesis. The bonding and structure of the as‐synthesized coatings were characterized using Fourier transform infrared and 1H NMR spectroscopies. The surface morphology and composition of the coatings were also assessed using scanning electron microscopy and energy‐dispersive X‐ray analysis. It was observed that changes in morphology occurred which had a marked and significant effect on the electrochemical behaviour of the coated LN SS confirmed using electrochemical techniques of potentiodynamic polarization and electrochemical impedance spectroscopy in aqueous 0.5 mol L−1 H2SO4 solution. The obtained results revealed that the copolymer coatings on LN SS provided significant corrosion protection in the acid medium. It was also found that a 1:1 ratio of indole to thiophene yielded the most stable and corrosion‐protective copolymer coating. © 2013 Society of Chemical Industry
Peculiarities in the pressure dependence of photoluminescence in InAlN
Authors: Kaminska Agata , Nowakowski Piotr , Staszczak Grzegorz , Suski Tadeusz , Suchocki Andrzej , Carlin Jean‐François , Grandjean Nicolas , Martin Robert , Yamamoto Akio
Published: April 2013

Studies of ambient‐pressure and high‐pressure behavior of photoluminescence (PL) for series of InxAl1−xN layers are presented. The measured evolution of PL energy (EPL) with x is characterized by a clear decrease of EPL and exhibits a strong bowing. This dependence corresponds to the predictions of ab initio calculations of the band‐gap energy changes EG with x. However, values of EPL are clearly lower than EG, for 0<x<0.3. For higher x, the measured EPL follows well the calculated EG. The experimentally determined pressure coefficient of PL energy (dEPL/dp) shows a complicated behavior for alloys with different In‐content. We found a strong reduction of dEPL/dp for 0<x<0.3 and a relatively constant magnitude of this coefficient for higher x. Moreover, for the lower x region, we observed dEPL/dp that can differ even by a factor two in samples with nominally very similar In‐content. The general tendency in dEPL/dp evolution with x corresponds to lower values than calculated dEG/dp for alloys with non‐uniform indium distribution. We propose two not necessary independent explanations of these experimental findings. First, due to non‐uniform In distribution (induced, e.g. by defects or non‐homogeneous strain) both EPL and dEPL/dp are reduced. Second, a similar behavior results from an involvement of the localized states, whose formation and contribution to PL can be induced by strain and/or native defects. In both hypotheses, the strain/defect density can significantly change around x ≈ 0.18 where InxAl1−xN layers are lattice matched to GaN template.
High frequency noise of epitaxial graphene grown on sapphire
Authors: Ardaravicˇius L. , Liberis J. , Šermukšnis E. , Matulionis A. , Hwang J. , Kwak J. Y. , Campbell D. , Alsalman H. A. , Eastman L. F. , Spencer M. G.
Published: April 2013

Microwave noise technique is applied to study in‐plane electronic properties of epitaxial graphene grown on sapphire by chemical vapor deposition and subjected to high electric field applied in the plane. The noise spectrum is measured in the field direction at room temperature. While a 1/f1.25‐type dependence is observed in the 200 MHz–2.5 GHz band, a shot noise contribution is resolved at 10 GHz. The shot noise is possibly associated with hole jumps across the potential barriers located in the graphene layer. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)