bluuebunny/crossref_metadata_2025_split huggingface dataset:
Sexual homicide in the USA committed by juveniles and adults, 1976–2007: Age of arrest and incidence trends over 32 years
Authors: Myers Wade C. , Chan Heng Choon ( Oliver) , Mariano Timothy Y. 
Published: December 2014

AbstractBackgroundReliable epidemiological data on sexual homicide are sparse, especially on trends in its incidence over time and age at arrest.AimsOur main aims were to study age at arrest and incidence trends for sexual homicide in the USA over about three decades (1976–2007).MethodsWe conducted longitudinal analyses of data from the largest USA homicide database available for the years 1976–2007.ResultsThe mean age at arrest for a sexual homicide was 26.3 years (range 7–76; modal 21 years). Three quarters of these offenders were young adults aged 18–35. Age at probable first arrest for a sexual homicide rose significantly from a mean of 25 to a mean of 29 years over the study period. The last decade of the three studied accounted for just one quarter of the homicides as charged in the whole period, but the proportion of sexual homicides specifically fell with each decade, so that the first period accounted for 56% of those in the whole period, the second for 33% and the final decade for just 11%. This was reflected in a reduction in the proportion of all homicides that were sexual, from 1.4% in the first decade to 0.8% in the second and 0.4% in the third, declining by a factor of five for adults and seven for juveniles.ConclusionsUse of official national criminal statistics has limitations in studying the epidemiology of any particular behaviour. Nonetheless, our findings of falling sexual homicide rates and of changes in at least one important demographic of these killers indicate a need for a considered reappraisal of such crimes. Establishment of accurate epidemiology and a study of associated factors may assist in the improvement of investigative and preventive strategies. Copyright © 2014 John Wiley & Sons, Ltd.
Solvent‐Free One‐Step Photochemical Hydroxylation of Benzene Derivatives by the Singlet Excited State of 2,3‐Dichloro‐5,6‐dicyano‐p‐benzoquinone Acting as a Super Oxidant
Authors: Ohkubo Kei , Hirose Kensaku , Fukuzumi Shunichi 
Published: December 2014

AbstractPhotoinduced hydroxylation of neat deaerated benzene to phenol occurred under visible‐light irradiation of 2,3‐dichloro‐5,6‐dicyano‐p‐benzoquinone (DDQ), which acts as a super photooxidant in the presence of water. Photocatalytic solvent‐free hydroxylation of benzene derivatives with electron‐withdrawing substituents such as benzonitrile, nitrobenzene, and trifluoromethylbenzene used as neat solvents has been achieved for the first time by using DDQ as a super photooxidant to yield the corresponding phenol derivatives and 2,3‐dichloro‐5,6‐dicyanohydroquinone (DDQH2) in the presence of water under deaerated conditions. In the presence of dioxygen and tert‐butyl nitrite, the photocatalytic hydroxylation of neat benzene occurred with DDQ as a photocatalyst to produce phenol. The photocatalytic reactions are initiated by oxidation of benzene derivatives with the singlet and triplet excited states of DDQ to form the corresponding radical cations, which associate with benzene derivatives to produce the dimer radical cations, which were detected by the femto‐ and nanosecond laser flash photolysis measurements to clarify the photocatalytic reaction mechanisms. Radical cations of benzene derivatives react with water to yield the OH‐adduct radicals. On the other hand, DDQ.− produced by the photoinduced electron transfer from benzene derivatives reacts with the OH‐adduct radicals to yield the corresponding phenol derivatives and DDQH2. DDQ is recovered by the reaction of DDQH2 with tert‐butyl nitrite when DDQ acts as a photocatalyst for the hydroxylation of benzene derivatives by dioxygen.
Simple Access to Highly Functional Bicyclic γ‐ and δ‐Lactams: Origins of Chirality Transfer to Contiguous Tertiary/Quaternary Stereocenters Assessed by DFT
Authors: Le Goff Ronan , Martel Arnaud , Sanselme Morgane , Lawson Ata Martin , Daïch Adam , Comesse Sébastien 
Published: December 2014

AbstractThis paper describes the synthesis of both polysubstituted oxazolo‐pyrrolidinones and ‐piperidinones by a domino process. The methodology is based on the reaction between hydroxyl halogenoamides and Michael acceptors, which leads efficiently to bicyclic lactams. The process is compatible with unsymmetrical electron‐withdrawing groups on the Michael acceptor, which allows the formation of two contiguous and fully controlled tertiary and quaternary stereocenters. In the case of tetrasubstituted Michael acceptors, two adjacent quaternary stereocenters are formed in good yield. Starting from (R)‐phenylglycinol derived amides results in the formation of enantioenriched bicyclic lactams in low to good yields and with high levels of stereoselectivity, thus greatly increasing the scope and interest of this strategy. The origins of chirality transfer and diastereoselectivity were studied by DFT calculations and have been attributed to a kinetic control in one of the last two steps of the reaction sequence. This selectivity is dependent upon both the substituents on the Michael acceptor and the sodium cation chelation.
Leadership effectiveness and motivation in Africa and the African Diaspora (LEAD): An introduction
Authors: Lituchy Terri R. , Punnett Betty Jane 
Published: December 2014

AbstractThe LEAD research project was developed in order to broaden management research in areas such as Africa. This special issue brings together the early findings of the research team. The present article reviews the literature and discusses the importance of understanding organizational leadership and motivation in under researched areas of the world. We explain the use of both emic (Delphi Technique and focus groups) and etic (large scale survey) research and describe the LEAD project and methodology in detail. Here we advocate the use of emic and etic research, and also consider the practical realities of using such approaches. Copyright © 2014 ASAC. Published by John Wiley & Sons, Ltd.
Introducing WLab—Going from Wpt (Waypoint) to a uniform material color equivalency space
Authors: Derhak Maxim W. , Berns Roy S. 
Published: December 2014

AbstractA set of invertible non‐linear transforms was derived that adjusts Wpt (Waypoint) coordinates (based on Wpt normalization) to and from a perceptually more uniform coordinate system (WLab or Waypoint‐Lab) than that provided by Wpt that allows for the advantageous features of Wpt to be directly applied to situations where other standard color spaces are typically used. The proposed transformations were found by optimizing for perceptual uniformity over both large and small color difference scales. The Munsell color order system was used as a representation for optimizing large‐scale perceptual uniformity. Correlations with Munsell value, chroma and hue along with comparisons with CIELAB and CAM02‐UCS were used to correct and assess overall large‐scale uniformity. The ΔE*94 color difference formula was used for optimization purposes for small‐scale uniformity. A STRESS analysis was applied to compare color differences based on Euclidean WLab distances with color differences based upon ΔE*ab, ΔE*94, ΔE00, DIN99o, CIECAM02, and CAM02‐UCS. It was found that WLab is a reasonably uniform material color equivalency space with small Euclidean WLab distances not being statistically different from ΔE*94, ΔE00, and Euclidean distances of DIN99o and CAM02‐UCS under reference observing conditions. © 2014 Wiley Periodicals, Inc. Col Res Appl, 40, 550–563, 2015
Catalytic Synthesis of Bi‐ and Teraryls in Aqueous Medium with Palladium(II) Complexes of 2‐(Pyridine‐2‐ylmethylsulfanyl)benzoic Acid
Authors: Prakash Om , Joshi Hemant , Sharma Kamal Nayan , Sharma Alpesh Kumar , Singh Ajai K. 
Published: December 2014

AbstractSuzuki–Miyaura coupling reactions of phenylboronic and 1,4‐phenylenediboronic acid with ArBr to form bi‐ and teraryls have been efficiently catalyzed by the air‐ and moisture‐insensitive complexes [PdCl2L1] [1, L1 = 2‐(pyridine‐2‐ylmethyl)sulfanylbenzoic acid; 0.05–0.5 mol‐%] and [Pd(L2‐H)2] (2, L2‐H = 2‐pyridin‐2‐yl‐benzo[b]thiophen‐3‐ol; 0.01–0.5 mol‐%). The complexes were formed by the reaction of [Pd(CH3CN)2Cl2] with L1, and the catalysis proceeds in water for 1. The loading of 0.1–0.5 mol‐% of Pd is very promising for the coupling reactions to form teraryls. The COOH group imparts solubility to 1 in water. Ligand L2 is formed by the unprecedented cyclization of L1 in the course of the complexation reaction. The yield of 2 increases with the reaction time (5 h: 70 %; 24 h: 85 %). The two complexes and L1 have been characterized by NMR spectroscopy (1H and 13C{1H}). The single‐crystal structures of 1 and 2 have been solved, and the Pd–S, Pd–N, and Pd–O bond lengths are 2.269(2), 1.999(6)–2.057(2), and 1.9787(17) Å, respectively. Nanoparticles (NPs) with a narrow size distribution (ca. 3.0–5.5 nm for 80–85 % of the particles) formed at the start of these reactions and appear to be important for the catalytic coupling. Poisoning experiments and a two‐phase test have shown that the catalysis is largely homogeneous and involves [Pd0–PdII] processes. The bond lengths and angles calculated by DFT are consistent with the experimental ones.
1,8‐Disubstituted Xanthylidene‐Based Remote Carbenes: Photolytic Generation and Isolation of Low‐Coordinate Palladium(II) Complex
Authors: Sugawara Shun , Abe Manabu , Fujiwara Yoshihisa , Wakioka Masayuki , Ozawa Fumiyuki , Yamamoto Yohsuke 
Published: December 2014

AbstractThe isolation and study of carbenes with σ‐donating and π‐accepting properties stronger than those of N‐heterocyclic carbenes (NHCs) have been regarded as one of the big challenges in carbene chemistry. We have investigated the properties of 1,8‐disubstituted xanthylidene‐based compounds by using two different approaches: The photolysis‐induced formation of free carbenes and the synthesis of the corresponding metal–carbene complexes by oxidative addition. The former study revealed that the carbene unsubstituted at the 1‐ and 8‐positions is kinetically more reactive than the parent xanthylidene and that the substituents at the 1‐ and 8‐positions are less effective in generating carbenes by photolysis. However, oxidative addition of palladium(0) to the 1,8‐diphenyl‐substituted precursor successfully afforded a low‐coordinate 14‐electron palladium(II)–carbene complex. This unusual complex is stabilized by agnostic interactions involving an adjacent phenyl group. This complex is the second example of a stable cationic 14‐electron palladium(II)–carbene complex to have been reported so far.
Diastereoselective Synthesis of Spirocyclic Dihydrofurans and 1‐Oxaspiro[4.5]decan‐6‐one Derivatives from Norbornyl α‐Diketones
Authors: Mahadevegowda Surendra H. , Khan Faiz Ahmed 
Published: December 2014

AbstractA diastereoselective zinc‐mediated propargylation of non‐enolizable norbornyl α‐diketones and an efficient AgI‐catalyzed cycloisomerization of the resulting α‐keto homopropargyl alcohols with terminal alkynes leading to spirocyclic dihydrofurans have been reported. The dihydrofurans obtained were subjected to hydrogenation to afford spiro tetrahydrofuran derivatives in nearly quantitative yields (98–99 %). Eventually, the prepared α‐spiro tetrahydrofuran norbornyl monoketones were utilized as precursors for acid‐mediated Grob‐type fragmentation reactions and converted into 1‐oxaspiro[4.5]decan‐6‐one derivatives by treatment with p‐toluenesulfonic acid.
Normal laser‐evoked cortical responses in patients with chronic hemibody pain
Authors: Kirveskari E. , Vartiainen N.V. , Kallio‐Laine K. , Kalso E. , Forss N. 
Published: December 2014

AbstractBackgroundPatients with widespread unilateral chronic pain associated with recurrent herpes simplex virus (HSV) infections show functional and/or structural changes in the insula, anterior cingulate cortex, frontal and prefrontal cortices, as well as the thalamus, suggesting central dysfunction of the pain system in these patients. Central pain has been associated with attenuated laser‐evoked cortical responses. We aimed to clarify whether the observed deficient activation of these areas to acute nociceptive stimuli is due to a lesion at a lower level of pain processing pathways.MethodsWe explored the functional integrity of the ascending nociceptive pathways by recording the cortical‐evoked responses to noxious laser stimulation using magnetoencephalography and electroencephalography in eight patients (age 41–51 years, mean 46) with recurrent HSV infections and a history of chronic, spontaneous, widespread unilateral pain, and in nine age‐matched healthy control subjects.ResultsThe cortical‐evoked fields of the HSV patients originating from the secondary somatosensory and posterior parietal cortices, as well as the evoked potentials recorded from the midline, did not differ from those of the control subjects, indicating functionally intact ascending nociceptive pathways.ConclusionsThe present results show that our patients with chronic hemibody pain do not show signs of spinothalamic tract lesion. This indicates normal processing of sensory aspects of painful stimuli, while higher pain processing areas show altered activation. We conclude that normal laser‐evoked magnetic fields (LEF) or laser‐evoked potentials (LEP) may not exclude central pain condition.
Numerical models of continental and submarine erosion: application to the northern Ligurian Margin (Southern Alps, France/Italy)
Authors: Petit Carole , Migeon Sébastien , Coste Marianne 
Published: December 2014

AbstractWe present a new numerical surface process model allowing us to take into account submarine erosion processes due either to submarine landslides or to hyperpycnal currents. A first set of models show that the frequency of hyperpycnal flows influences the development of submarine canyons at the mouth of continental rivers. Further experiments show that an increase in submarine slope leads to faster regressive canyon erosion and a more dentritic canyon network, whereas increasing the height of the unstable sediment pile located on the shelf break leads to wider and less dendritic canyons. The models are then applied to the western segment of the north Ligurian margin (northwestern Mediterranean), which displays numerous submarine canyons with various sizes and morphologies. From west to east, canyon longitudinal profiles as well as margin‐perpendicular profiles progressively change from moderately steep, concave‐up shapes to steeper linear to convex‐up shapes suggesting increasing eastward margin uplift. Moreover, the foot of the margin is affected by a marked slope increase with evidences of mass transport due to landslides. Numerical models which reproduce well the North Ligurian margin morphologic features indicate that the western part of the margin is submitted to rather low (i.e. 0.4 mm yr−1) uplift and intense submarine erosion due to frequent hyperpycnal currents, whereas the eastern part bears more rapid (i.e. 0.7 mm yr−1) uplift and has little or no hyperpycnal currents. Copyright © 2014 John Wiley & Sons, Ltd.
Sweden's first forest hydrology field study 1905–1926: contemporary relevance of inherited conclusions and data from the Rokliden Hillslope
Authors: Grip Harald 
Published: December 2014

AbstractDuring the last decades of the 19th century, a great worry arose about forest landscape paludification in Northern Sweden. This was the original impetus for forest hydrological research in Sweden, and the Swedish Institute of Experimental Forestry established the first field research site in 1905 at Rokliden, close to Piteå in North Sweden. It comprised 8.64 ha located 2 km down a 3‐km‐long gently sloping (~4%), north facing Norway spruce covered till slope, interspersed with small mires. By 1931, it was concluded that paludification was not spreading across Northern Sweden at an appreciable rate. Within the Rokliden research site, 22 groundwater wells were installed and levels measured weekly until 1926. A map with 0.5 m equidistance, ten vegetation classes, and soil profiles was established. Groundwater flow velocity was estimated by tracing added sodium chloride. Hydraulic conductivity was measured on undisturbed soil cores, while mechanical and chemical analyses were carried out on other samples. Groundwater was collected and analysed for dissolved compounds including oxygen. Hydrology was found important for soil types and vegetation development. The necessary profile drainage for podzol soil development was identified as vein drainage at the bedrock surface. Modern measurements in the re‐established groundwater observation network and re‐analysis of old data confirmed the plausibility of these original conclusions. Partial catchment area could explain rates of both groundwater level rise and recession. Revisiting this field study reveals that many issues in contemporary hillslope hydrology were already established a century ago, even though the provenance of that knowledge is not generally recognized. Copyright © 2014 John Wiley & Sons, Ltd.
Combined exposure to lead, inorganic mercury and methylmercury shows deviation from additivity for cardiovascular toxicity in rats
Authors: Wildemann Tanja M. , Weber Lynn P. , Siciliano Steven D. 
Published: December 2014

AbstractEnvironmental exposure to metal mixtures in the human population is common. Mixture risk assessments are often challenging because of a lack of suitable data on the relevant mixture. A growing number of studies show an association between lead or mercury exposure and cardiovascular effects. We investigated the cardiovascular effects of single metal exposure or co‐exposure to methylmercury [MeHg(I)], inorganic mercury [Hg(II)] and lead [Pb(II)]. Male Wistar rats received four different metal mixtures for 28 days through the drinking water. The ratios of the metals were based on reference and environmental exposure values. Blood and pulse pressure, cardiac output and electrical activity of the heart were selected as end‐points. While exposure to only MeHg(I) increased the systolic blood pressure and decreased cardiac output, the effects were reversed with combined exposures (antagonism). In contrast to these effects, combined exposures negatively affected the electrical activity of the heart (synergism). Thus, it appears that estimates of blood total Hg levels need to be paired with estimates of what species of mercury dominate exposure as well as whether lead co‐exposure is present to link total blood Hg levels to cardiovascular effects. Based on current human exposure data and our results, there may be an increased risk of cardiac events as a result of combined exposures to Hg(II), MeHg(I) and Pb(II). This increased risk needs to be clarified by analyzing lead and Hg exposure data in relation to cardiac electrical activity in epidemiological studies. Copyright © 2014 John Wiley & Sons, Ltd.
Heterogeneous neuromuscular activation within human rectus femoris muscle during pedaling
Authors: Watanabe Kohei , Kouzaki Motoki , Moritani Toshio 
Published: December 2014

ABSTRACTIntroduction: We investigated the effect of workload and the use of pedal straps on the spatial distribution of neuromuscular activation within the rectus femoris (RF) muscle during pedaling movements. Methods: Eleven healthy men performed submaximal pedaling exercises on an electrically braked ergometer at different workloads and with or without pedal straps. During these tasks, surface electromyograms (SEMGs) were recorded from the RF using 36 electrode pairs, and central locus activation (CLA) was calculated along the longitudinal line of the muscle. Results: CLA moved markedly, indicating changes in spatial distribution of SEMG within the muscle, during a crank cycle under all conditions (P < 0.05). There were significant differences in CLA among different workloads and between those with and without pedal straps (P < 0.05). Conclusion: These results suggest that neuromuscular activation within the RF is regulated regionally by changes in workload and the use of pedal straps during pedaling. Muscle Nerve 52:404–411, 2015
Exact and approximate solutions to LQG homing problems in one and two dimensions
Authors: Lefebvre Mario , Zitouni Foued 
Published: December 2014

SummaryStochastic optimal control problems in which two‐dimensional diffusion processes are controlled until they enter a given set are solved explicitly. When symmetry can be used, exact solutions are obtained. The same arguments are valid for one‐dimensional processes. In the general case, it is shown how to obtain good approximate solutions. Various examples are presented.
Photo‐induced controlled radical polymerization of methyl methacrylate mediated by photosensitive nitroxides
Authors: Su Jiahui , Liu Xiaoxuan , Hu Junqi , You Qin , Cui Yanyan , Chen Yingyin 
Published: December 2014

AbstractPhotosensitive nitroxides bearing different chromophore groups (benzophenone, naphthalene and quinoline) were synthesized and characterized. The photochemical properties of the synthesized products were investigated by UV−visible and fluorescence measurements. The results indicated that an efficient energy transfer from the chromophore moiety to the nitroxide radical moiety could occur within the molecular distances. The photo‐induced nitroxide‐mediated polymerization of methyl methacrylate (MMA) was performed using the photosensitive nitroxide/2,2‐dimethoxy‐2‐phenyl acetophenone as a bimolecular mediated system. The controlled character of the polymerization was confirmed by the linear tendency of molecular weight evolution with narrow molecular weight distribution (1.3−1.4). The experimental conditions, such as type of chromophore, initiator concentration and molar ratio of initiator/nitroxide, are discussed for a better understanding of the mechanism of the controlled polymerization. Using the polymerization products as macroinitiator, the chain extension reaction of MMA turned out to be able to re‐initiate further polymerization of the monomer. © 2014 Society of Chemical Industry
Shear behaviour of composite dowels in transversely cracked concrete
Authors: Classen Martin , Herbrand Martin 
Published: December 2014

AbstractIn steel‐concrete composite girders, innovative composite dowels can be used to transfer the shear forces between the concrete slab and the steel section. Today, composite dowels are predominately used in engineering structures such as prefabricated composite bridges. However, due to their ease of manufacture, good loadbearing and deformation properties and suitability for slender concrete slabs, these composite dowels are being used more than ever in building construction as well. The present article describes shear tests on puzzle‐shaped composite dowels for slender concrete slabs with a depth of only 10 cm. Aside from different reinforcement configurations, the influence of different longitudinal stress states and transverse cracking in the concrete slab have been investigated. In previous studies of the shear force capacity of composite dowels, the influence of transverse cracking has been neglected. However, our own experiments described in this paper show that the shear capacity of composite dowels is significantly affected by concrete cracking. In order to simulate the experiments performed and to analyse the shear behaviour of the composite dowels in cracked and uncracked concrete, a three‐dimensional, non‐linear finite element model of the shear tests was set up. The results of both the experimental and numerical investigations are summarized in this paper.