bluuebunny/crossref_metadata_2025 huggingface dataset:
A configurable 2‐Gbps LVDS transceiver in 150‐nm CMOS with pre‐emphasis, equalization, and slew rate control
Authors: Jawed Syed Arsalan , Asghar Ali , Khan Khubaib , Abbasi Shahbaz , Naveed Muhammad , Siddiqi Yasir , Siddiqi Waqas
Published: November 2016

A configurable full‐duplex low‐voltage differential signaling transceiver is presented, which can be configured to operate either for smaller differential channels (a few inches of striplines) or for longer channels (10 m of twisted pair cables). The configurability is embedded in the form of functionalities like pre‐emphasis, equalization, and slew rate control within the transceiver. The transmitter employs a hybrid voltage–current‐mode driver, which due to replica action, achieves a high‐impedance current‐mode signal dispatch and at the same time provides a matched impedance at the near end for improved intersymbol interference. The transmitter achieves slew rate control through a band‐limited pre‐driver, while the pre‐emphasis is achieved through a capacitive feed‐forward. The receiver employs a large‐input common‐mode first stage enclosed in a common‐mode control loop that enables its first stage to also act like a domain shifter (VDDIO‐to‐VDDCORE) reducing the overall power consumption. The equalization in the receiver is implemented by using carefully sized active inductive loads inside the receiver. The transceiver is designed and fabricated in 150‐nm complementary metal–oxide–semiconductor, sharing the space with a larger die, occupying an area of 400 × 400μm. The measurement results demonstrate that the transceiver is operating at 2 Gbps both for a 4‐in microstrip and a 10‐m twisted pair CAT6 cable with 30 and 180 ps of total jitter, respectively. The built‐in impedance calibrator minimizes the spread in the on‐die termination at the near end provided by the transmitter‐minimizing bit error rate across process, voltage, and temperature corners. The transmitter consumes a total power of 17 mW operating at 2 Gbps, that is, 8.5 pJ/bit of energy consumption; the receiver consumes a total power of 3.5 mW while driving a load of 5 pF at 2 Gbps. Copyright © 2016 John Wiley & Sons, Ltd.
A three‐vector‐based direct power control strategy for three‐phase voltage source PWM converters
Authors: Wang Meng , Shi Yanyan , Qi Mingyan , Shen Minghui
Published: November 2016

For traditional direct power control strategy, there exist high steady‐state power ripples and large current harmonics. To solve this problem, this work proposes a novel three‐vector‐based direct power control strategy for three‐phase voltage source pulse‐width‐modulated (PWM) converters. Different from traditional predictive direct power control strategy, an improved vector table is presented and three voltage vectors are selected, which considers the impact of voltage vectors on the active and reactive power simultaneously. The performance of the three‐phase voltage source PWM converters with the proposed control strategy is investigated and compared with the predictive deadbeat direct power control strategy. Furthermore, the three‐phase voltage source PWM converters have also been tested in the condition of different loads and when voltage unbalance occurs. Simulation and experimental work are conducted. The results conclude that the proposed strategy is of simple structure and fast dynamic response. Besides, it can effectively reduce steady‐state power ripples and current harmonics, improving the performance of the three‐phase PWM converters. Copyright © 2016 John Wiley & Sons, Ltd.
Disturbance‐mediated heterogeneity drives pollinator diversity in boreal managed forest ecosystems
Authors: Rodríguez Antonio , Kouki Jari
Published: November 2016

Intensive forest management, together with fire suppression, have decreased structural complexity and altered dynamics of boreal forests profoundly. Such management threatens forest biodiversity and can reduce the provision of ecosystem services. Although the importance of ecosystem services is widely acknowledged, conservation strategies are hindered by poor knowledge about diversity patterns of service provider species as well as on mechanisms affecting these assemblages at different spatial and temporal scales. In this study, we assessed the effect of disturbance management on forest pollinator communities. To do so, we used a large‐scale ecological experiment conducted in the year 2000, where forest complexity was manipulated with different harvest regimes and prescribed fire. Results were consistent with a positive response of pollinators to increasing habitat heterogeneity driven by past disturbances. Harvested sites harbored a diverse pollinator community, and showed higher spatial and temporal turnover in species richness. Conversely, old‐growth forest communities were a nested subset of harvested sites and contained half of their total diversity. Variation in community composition (β diversity) was primarily affected by species temporal turnover. Throughout the season, β diversity was controlled by fire and harvesting legacies, which provide environmental heterogeneity in the form of flowering and nesting resources over space and time. Conservation strategies may undervalue ecosystem services in dynamic, naturally disturbance‐driven, landscapes when relying solely on undisturbed forests areas. However, maintaining natural dynamics in early successional forests, by emulating natural disturbances at harvesting, hold promise for the conservation of both biodiversity and ecosystem services in boreal forests.
Direct and indirect costs among patients with binge‐eating disorder in the United States
Authors: Ling You‐Li , Rascati Karen L. , Pawaskar Manjiri
Published: November 2016

Objective

To quantify the economic burden of binge‐eating disorder (BED) in terms of work productivity loss, healthcare resource utilization, and healthcare costs.

Methods

Respondents of the US National Health and Wellness Survey 2013 were invited to participate in a follow‐up internet survey to identify adults with BED using DSM‐5 criteria. Work productivity loss, healthcare resource utilization, and direct and indirect costs were assessed for BED respondents and matched non‐BED respondents using generalized linear models or two‐part models as appropriate.

Results

A total of 1,720 people were included in our analysis (N = 344 with BED; N= 1,376 without BED). BED respondents had higher levels of activity impairment than non‐BED respondents (41.29% vs. 23.18%, p < .001). Employed BED respondents (N = 178) had a greater level of work impairment than employed non‐BED respondents (N = 686) (36.83% vs. 14.41%, p = .009). Higher healthcare resource utilization in the past 6 months among BED respondents was reported than matched non‐BED respondents: numbers of surgeries (0.23 vs. 0.13, p = .021), ER visits (0.26 vs. 0.15, p = .016), and physician visits (6.09 vs. 4.56, p = .002). BED respondents reported higher total direct costs than matched non‐BED respondents ($20,194 vs. $14,465, p = .005). The indirect costs among employed BED respondents were also higher than those without BED ($19,327 vs. $9,032, p < .001).

Discussion

Individuals with BED reported significantly greater economic burden with respect to work productivity loss, level of healthcare resource utilization, and costs compared to non‐BED respondents. © 2016 Wiley Periodicals, Inc.(Int J Eat Disord 2017; 50:523–532)
Predictors of dropout in face‐to‐face and internet‐based cognitive‐behavioral therapy for bulimia nervosa in a randomized controlled trial
Authors: Watson Hunna J. , Levine Michele D. , Zerwas Stephanie C. , Hamer Robert M. , Crosby Ross D. , Sprecher Caroline S. , O'Brien Amy , Zimmer Benjamin , Hofmeier Sara M. , Kordy Hans , Moessner Markus , Peat Christine M. , Runfola Cristin D. , Marcus Marsha D. , Bulik Cynthia M.
Published: November 2016

Objective

We sought to identify predictors and moderators of failure to engage (i.e., pretreatment attrition) and dropout in both Internet‐based and traditional face‐to‐face cognitive‐behavioral therapy (CBT) for bulimia nervosa. We also sought to determine if Internet‐based treatment reduced failure to engage and dropout.

Method

Participants (N = 191, 98% female) were randomized to Internet‐based CBT (CBT4BN) or traditional face‐to‐face group CBT (CBTF2F). Sociodemographics, clinical history, eating disorder severity, comorbid psychopathology, health status and quality of life, personality and temperament, and treatment‐related factors were investigated as predictors.

Results

Failure to engage was associated with lower perceived treatment credibility and expectancy (odds ratio [OR] = 0.91, 95% CI: 0.82, 0.97) and body mass index (BMI) (OR = 1.10; 95% CI: 1.03, 1.18). Dropout was predicted by not having a college degree (hazard ratio [HR] = 0.55; 95% CI: 0.37, 0.81), novelty seeking (HR = 1.02; 95% CI: 1.01, 1.03), previous CBT experience (HR = 1.77; 95% CI: 1.16, 2.71), and randomization to the individual's nonpreferred treatment format (HR = 1.95, 95% CI: 1.28, 2.96).

Discussion

Those most at risk of failure to engage had a higher BMI and perceived treatment as less credible and less likely to succeed. Dropout was associated with less education, higher novelty seeking, previous CBT experience, and a mismatch between preferred and assigned treatment. Contrary to expectations, Internet‐based CBT did not reduce failure to engage or dropout. © 2016 Wiley Periodicals, Inc.(Int J Eat Disord 2017; 50:569–577)
Soil phosphorus heterogeneity promotes tree species diversity and phylogenetic clustering in a tropical seasonal rainforest
Authors: Xu Wumei , Ci Xiuqin , Song Caiyun , He Tianhua , Zhang Wenfu , Li Qiaoming , Li Jie
Published: November 2016

The niche theory predicts that environmental heterogeneity and species diversity are positively correlated in tropical forests, whereas the neutral theory suggests that stochastic processes are more important in determining species diversity. This study sought to investigate the effects of soil nutrient (nitrogen and phosphorus) heterogeneity on tree species diversity in the Xishuangbanna tropical seasonal rainforest in southwestern China. Thirty‐nine plots of 400 m2 (20 × 20 m) were randomly located in the Xishuangbanna tropical seasonal rainforest. Within each plot, soil nutrient (nitrogen and phosphorus) availability and heterogeneity, tree species diversity, and community phylogenetic structure were measured. Soil phosphorus heterogeneity and tree species diversity in each plot were positively correlated, while phosphorus availability and tree species diversity were not. The trees in plots with low soil phosphorus heterogeneity were phylogenetically overdispersed, while the phylogenetic structure of trees within the plots became clustered as heterogeneity increased. Neither nitrogen availability nor its heterogeneity was correlated to tree species diversity or the phylogenetic structure of trees within the plots. The interspecific competition in the forest plots with low soil phosphorus heterogeneity could lead to an overdispersed community. However, as heterogeneity increase, more closely related species may be able to coexist together and lead to a clustered community. Our results indicate that soil phosphorus heterogeneity significantly affects tree diversity in the Xishuangbanna tropical seasonal rainforest, suggesting that deterministic processes are dominant in this tropical forest assembly.
Cellular and humoral immunity in a wild mammal: Variation with age & sex and association with overwinter survival
Authors: Watson Rebecca L. , McNeilly Tom N. , Watt Kathryn A. , Pemberton Josephine M. , Pilkington Jill G. , Waterfall Martin , Hopper Phoebe R.T. , Cooney Daniel , Zamoyska Rose , Nussey Daniel H.
Published: November 2016

Immune defenses are expected to be crucial for survival under the considerable parasite pressures experienced by wild animals. However, our understanding of the association between immunity and fitness in nature remains limited due to both the complexity of the vertebrate immune system and the often‐limited availability of immune reagents in nonmodel organisms. Here, we use methods and reagents developed by veterinary researchers for domestic ungulates on blood samples collected from a wild Soay sheep population, to evaluate an unusually broad panel of immune parameters. Our evaluation included different innate and acquired immune cell types as well as nematode parasite‐specific antibodies of different isotypes. We test how these markers correlate with one another, how they vary with age‐group and sex, and, crucially, whether they predict overwinter survival either within or among demographic groups. We found anticipated patterns of variation in markers with age, associated with immune development, and once these age trends were accounted for, correlations among our 11 immune markers were generally weak. We found that females had higher proportions of naïve T cells and gamma–delta T cells than males, independent of age, while our other markers did not differ between sexes. Only one of our 11 markers predicted overwinter survival: sheep with higher plasma levels of anti‐nematode IgG antibodies were significantly more likely to survive the subsequent high mortality winter, independent of age, sex, or weight. This supports a previous finding from this study system using a different set of samples and shows that circulating antibody levels against ecologically relevant parasites in natural systems represent an important parameter of immune function and may be under strong natural selection. Our data provide rare insights into patterns of variation among age‐ and sex groups in different T‐cell subsets and antibody levels in the wild, and suggest that certain types of immune response—notably those likely to be repeatable within individuals and linked to resistance to ecologically relevant parasites—may be most informative for research into the links between immunity and fitness under natural conditions.
100 years of ecology: what are our concepts and are they useful?
Authors: Reiners William A. , Lockwood Jeffrey A. , Reiners Derek S. , Prager Steven D.
Published: November 2016

On the occasion of the Ecological Society of America's centennial, we sought to learn which ecological concepts members value in terms of their utility. This required defining “concept,” and selecting concepts from current ecology textbooks that might arguably belong to a normative set. AllESAmembers were invited to participate in an online survey in October 2014 in which they rated 70, randomly selected concepts (out of a total set of 131) in terms of utility. Alternative to rating, respondents could mark the concept as unfamiliar. Respondents were also able list concepts that were important to them that were not encountered in the survey. Fifteen percent (1324) of theESAmembership participated in the survey. Of these, 89% were addressed in North America, 62% were male, 77% held Ph.D. degrees, 67% were involved in academia through employment or as students, and about one‐half of the total were divided between community and ecosystem ecology domains of interest. The 10 highest ranked concepts (in descending order) for utility were scales (small, local, regional, global, etc.), ecosystem, habitat, species, disturbance/perturbation, organism, population, community, competition, and species life history. The 10 lowest ranked concepts (in descending order) for utility were Lotka‐Volterra predator–prey/competition models, Allee effect, nutrient spiraling, character displacement, doubling time, climax, Hardy‐Weinberg equation, red queen hypothesis, chemoautotroph/chemoautotrophy, and mimicry. Respondents entered 2800 terms not encountered in the survey. After parsing for concepts missed due to the survey's random presentation process, for semantic redundancy and for terms deemed non‐concepts, 119 candidate concepts emerged. Many of these deserve consideration for inclusion in a normative set and introduction in textbooks. This research provides a well‐considered definition of “concept,” a basis for defining a normative set of concepts expected to be known to all ecologists, and a measure of familiarity but, more importantly, a measure of usage by contemporary ecologists who were members ofESA. These results help us to understand ourselves and our science, to better teach ecology, to guide the initiatives of the collective ecological community, and to further explore the extent and intellectual structure of the principal concepts by which ecologists pursue their work.
Geographic variation in apparent competition between native and invasive Phragmites australis
Authors: Bhattarai Ganesh P. , Meyerson Laura A. , Cronin James T.
Published: November 2016

Apparent competition, the negative interaction between species mediated by shared natural enemies, is thought to play an important role in shaping the structure and dynamics of natural communities. However, its importance in driving species invasions, and whether the strength of this indirect interaction varies across the latitudinal range of the invasion, has not been fully explored. We performed replicated field experiments at four sites spanning 900 km along the Atlantic Coast of the United States to assess the presence and strength of apparent competition between sympatric native and invasive lineages of Phragmites australis. Four herbivore guilds were considered: stem‐feeders, leaf‐miners, leaf‐chewers and aphids. We also tested the hypothesis that the strength of this interaction declines with increasing latitude. Within each site, native and invasive plants of P. australis were cross‐transplanted between co‐occurring native and invasive patches in the same marsh habitat and herbivore damage was evaluated at the end of the growing season. Apparent competition was evident for both lineages and involved all but the leaf‐chewer guild. For native plants, total aphids per plant was 296% higher and the incidence of stem‐feeding and leaf‐mining herbivores was 34% and 221% higher, respectively, when transplanted into invasive than native patches. These data suggest that invasive P. australis has a negative effect on native P. australis via apparent competition. Averaged among herbivore types, the indirect effects of the invasive lineage on the native lineage was 57% higher than the reverse situation, suggesting that apparent competition was asymmetric. We also found that the strength of apparent competition acting against the native lineage was comparable to the benefits to the invasive lineage from enemy release (i.e., proportionately lower mean herbivory of the invasive relative to the native taxa). Finally, we found the first evidence that the strength of apparent competition acting against the native lineage (from stem‐feeders only) decreased with increasing latitude. These results suggest that not only could apparent competition be of tantamount importance to enemy release in enhancing the establishment and spread of invasive taxa, but also that these indirect and direct herbivore effects could vary over the invasion range.
Tropical fish community does not recover 45 years after predator introduction
Authors: Sharpe D. M. T. , De León L. F. , González R. , Torchin M. E.
Published: November 2016

Predation is considered to be an important factor structuring natural communities. However, it is often difficult to determine how it may influence long‐term, broad‐scale, diversity patterns, particularly in diverse tropical systems. Biological introductions can provide powerful insight to test the sustained consequences of predation in natural communities, if pre‐introduction data are available. Half a century ago, Zaret and Paine demonstrated strong and immediate community‐level effects following the introduction of a novel apex predator (peacock bass,Cichla monoculus) into Lake Gatun, Panama. To test for long‐term changes associated with this predator introduction, we followed up on their classic study by replicating historical sampling methods and examining changes in the littoral fish community at two sites in Lake Gatun 45 years post‐introduction. To broaden our inference, we complemented this temporal comparison with a spatial analysis, wherein we compared the fish communities from two lakes with and one lake without peacock bass. Comparisons with historical data revealed that the peacock bass remains the most abundant predator in Lake Gatun. Furthermore, the collapse of the littoral prey community observed immediately following the invasion has been sustained over the past 45 years. The mean abundance of native littoral fish is now 96% lower than it was prior to the introduction. Diversity (rarefied species richness) declined by 64% post‐introduction, and some native species appear to have been locally extirpated. We observed a similar pattern across invaded and uninvaded lakes: the mean abundance of native fishes was 5–40 times lower in lakes with (Gatun, Alajuela) relative to the lake without peacock bass (Bayano). In particular, small‐bodied native fishes (Characidae, Peociliidae), which are common prey of the peacock bass, were more than two orders of magnitude (307 times) less abundant in Gatun and one order of magnitude (28 times) less abundant in Alajuela than in Bayano. However, total native fish diversity did not differ significantly across lakes, suggesting that while many native species have declined in abundance, few have been completely extirpated. Introduced predators can have strong effects on community structure and functional diversity, even in highly diverse tropical communities, and these effects can persist over multiple decades.
Ecological functions provided by dung beetles are interlinked across space and time: evidence from 15N isotope tracing
Authors: Nervo Beatrice , Caprio Enrico , Celi Luisella , Lonati Michele , Lombardi Giampiero , Falsone Gloria , Iussig Gabriele , Palestrini Claudia , Said‐Pullicino Daniel , Rolando Antonio
Published: November 2016

Maintaining multiple ecological functions (“multifunctionality”) is crucial to sustain viable ecosystems. To date most studies on biodiversity‐ecosystem functioning (BEF) have focused on single or few ecological functions and services. However, there is a critical need to evaluate how species and species assemblages affect multiple processes at the same time, and how these functions are interconnected. Dung beetles represent excellent model organisms because they are key contributors to several ecosystem functions. Using a novel method based on the application of 15N‐enriched dung in a mesocosm field experiment, we assessed the role of dung beetles in regulating multiple aspects of nutrient cycling in alpine pastures over appropriate spatial (up to a soil depth of 20 cm) and temporal (up to 1 yr after dung application) scales. 15N isotope tracing allowed the evaluation of multiple interrelated ecosystem functions responsible for the cycling of dung‐derived nitrogen (DDN) in the soil and vegetation. We also resolved the role of functional group identity and the importance of interactions among co‐occurring species for sustaining multiple functions by focusing on two different dung beetle nesting strategies (tunnelers and dwellers). Species interactions were studied by contrasting mixed‐species to single‐species assemblages, and asking whether the former performed multiple functions better than the latter. Dung beetles influenced at least seven ecological functions by facilitating dung removal, transport of DDN into the soil, microbial ammonification and nitrification processes, uptake of DDN by plants, herbage growth, and changes in botanical composition. Tunnelers and dwellers were found to be similarly efficient for most functions, with differences based on the spatial and temporal scales over which the functions operated. Although mixed‐species assemblages seemed to perform better than single‐species, this outcome may be dependent on the context. Most importantly though, the different functions were found to be interconnected sequentially as reveled by analyzing 15N content in dung, soil and vegetation. Taken together, our current findings offer strong support for the contention that the link between biodiversity and ecosystem functions should be examined not function by function, but in terms of understanding multiple functions and how they interact with each other.
No strong evidence for increasing liana abundance in the Myristicaceae of a Neotropical aseasonal rain forest
Authors: Smith James R. , Queenborough Simon A. , Alvia Pablo , Romero‐Saltos Hugo , Valencia Renato
Published: November 2016

The “liana dominance hypothesis” posits that lianas are increasing in abundance in tropical forests, thereby potentially reducing tree biomass due to competitive interactions between trees and lianas. This scenario has implications not only for forest ecosystem function and species composition, but also climate change given the mass of carbon stored in tropical trees. In 2003 and 2013, all Myristicaceae trees in the 50‐ha Yasuní Forest Dynamics Plot, Ecuador, were surveyed for liana presence and load in their crowns. We tested the hypothesis that the proportion of trees with lianas increased between 2003 and 2013 in line with the liana dominance hypothesis. Contrary to expectations, the total proportion of trees with lianas decreased from 35% to 32%, and when only trees ≥10 cm diameter at breast height were considered liana incidence increased 44–48%. Liana load was dynamic with a large proportion of trees losing or gaining lianas over the 10‐yr period; large trees with intermediate liana loads increased in proportion at the expense of those with low and high loads. Lianas also impacted performance: trees with 26–75% crown cover by lianas in 2003 had reduced growth rates of 80% compared to of liana‐free trees, and trees with >75% crown cover had 33% the growth rate and a log odds of mortality eight times that of liana‐free trees. We suggest that the lack of strong support found for the liana dominance hypothesis is likely due to the aseasonal climate of Yasuní, which limits the competitive advantage lianas maintain over trees during dry seasons due to their efficient capture and use of water. We propose further research of long‐term liana dynamics from aseasonal forests is required to determine the generality of the increasing liana dominance hypothesis in Neotropical forests.
Dynamics of cerebral blood flow in patients with mild non‐ischaemic heart failure
Authors: Erkelens Christian D. , van der Wal Haye H. , de Jong Bauke M. , Elting Jan‐Willem , Renken Remco , Gerritsen Marleen , van Laar Peter Jan , van Deursen Vincent M. , van der Meer Peter , van Veldhuisen Dirk J. , Voors Adriaan A. , Luijckx Gert‐Jan
Published: November 2016

Aims

Heart failure (HF) is associated with tissue hypoperfusion and congestion leading to organ dysfunction. Although cerebral blood flow (CBF) is preserved over a wide range of perfusion pressures in healthy subjects, it is impaired in end‐stage HF. We aimed to compare CBF, autoregulation, and cognitive function in patients with mild non‐ischaemic HF with healthy controls.

Methods and results

Fifteen patients with mild idiopathic dilated cardiomyopathy and 15 matched healthy controls were studied. Co‐existing cerebrovascular disease was excluded. All subjects, except five patients with an implantable cardioverter defibrillator, underwent magnetic resonance imaging for measurements of both CBF by arterial spin labelling and quantitative volume flow entering the brain. Cardiocerebral vascular function was assessed with Doppler techniques testing cerebral dynamic autoregulation and vasomotor reactivity. Cognitive analysis was performed by neuropsychological testing. Global and regional CBF did not differ between HF patients (44.3 mL/100 g.min) and controls (42.1 mL/100 g.min). Basilar but not carotid artery inflow was reduced in patients (1.95 mL/s vs. 2.51 mL/s, P = 0.009). Testing autoregulation revealed fewer dampened blood flow fluctuations in HF patients vs. controls (0.96% vs. 0.67%, P < 0.001). Vasomotor reactivity in HF patients showed a reduced CBF velocity (48.4% vs. 61.0%, P = 0.05) and regional cerebral oxygen saturation (18.3% vs. 23.8%, P = 0.02). Cognitive function overall was not affected.

Conclusion

Although global CBF was unaffected in patients with mild HF, significant changes in basilar inflow volume, cerebral autoregulation and vasomotor reactivity were observed. We describe a model of dynamic cerebral mechanisms required to compensate for the impaired haemodynamics in early‐stage HF.
Peptidomic analysis of type 1 diabetes associated HLA‐DQ molecules and the impact of HLA‐DM on peptide repertoire editing
Authors: Zhou Zemin , Reyes‐Vargas Eduardo , Escobar Hernando , Chang Kuan Y. , Barker Adam P. , Rockwood Alan L. , Delgado Julio C. , He Xiao , Jensen Peter E.
Published: November 2016

HLA‐DM and class II associated invariant chain (Ii) are key cofactors in the MHC class II (MHCII) antigen processing pathway. We used tandem mass spectrometry sequencing to directly interrogate the global impact of DM and Ii on the repertoire of MHCII‐bound peptides in human embryonic kidney 293T cells expressing HLA‐DQ molecules in the absence or presence of these cofactors. We found that Ii and DM have a major impact on the repertoire of peptides presented by DQ1 and DQ6, with the caveat that this technology is not quantitative. The peptide repertoires of type 1 diabetes (T1D) associated DQ8, DQ2, and DQ8/2 are altered to a lesser degree by DM expression, and these molecules share overlapping features in their peptide binding motifs that are distinct from control DQ1 and DQ6 molecules. Peptides were categorized into DM‐resistant, DM‐dependent, or DM‐sensitive groups based on the mass spectrometry data, and representative peptides were tested in competitive binding assays and peptide dissociation rate experiments with soluble DQ6. Our data support the conclusion that high intrinsic stability of DQ‐peptide complexes is necessary but not sufficient to confer resistance to DM editing, and provide candidate parameters that may be useful in predicting the sensitivity of T‐cell epitopes to DM editing.
α4β1 integrin promotes accumulation of tissue‐resident memory CD8+ T cells in salivary glands
Authors: Woyciechowski Sandra , Hofmann Maike , Pircher Hanspeter
Published: November 2016

The salivary glands (SGs) of virus‐immune mice contain substantial numbers of tissue‐resident memory CD8+ T cells (TRM cells) that can provide immunity to local infections. Integrins regulate entry of activated T cells into nonlymphoid tissues but the molecules that mediate migration of virus‐specific CD8+ T cells to the SGs have not yet been defined. Here, we found that polyinosinic‐polycytidylic acid (poly(I:C)) strongly promoted the accumulation of P14 TCR‐transgenic CD8+ TRM cells in SGs in an α4β1 integrin‐dependent manner. After infection with lymphocytic choriomeningitis virus, accumulation of P14 TRM cells in SGs and intestine but not in kidney was also α4 integrin dependent. Blockade of α4β7 by monoclonal antibodies (mAbs) inhibited lymphocytic choriomeningitis virus‐induced accumulation of P14 TRM cells in the intestine but not in SGs. In conclusion, our data reveal that α4β1 integrin mediates CD8+ TRM accumulation in SGs and that poly(I:C) can be used to direct activated CD8+ T cells to this organ.
Photophysical Properties of Visible‐Light‐Harvesting PtII Bis(acetylide) Complexes
Authors: Yang Wenbo , Zhao Jianzhang
Published: November 2016

PtII complexes have attracted much attention due to their readily derivatizable molecular structures and efficient production of triplet excited states and have been extensively used in many areas. Conventional PtII complexes usually exhibit small molar absorption coefficients in the visible spectral region, and the triplet excited state lifetimes are short. However, for applications such as photocatalysis, triplet–triplet annihilation (TTA) upconversion, nonlinear optics, etc., visible‐light‐harvesting PtII bis(acetylide) complexes with long‐lived triplet excited state are cucial. We summarize strategies directed towards achieving these goals, through the attachment of appropriate strong visible‐light‐harvesting organic chromophores to the ligand to switch the S0→1MLCT (metal‐to‐ligand charge transfer) transition to the S0→1IL (intraligand) transition (π–π*) and to switch the lowest triplet excited state from the 3MLCT to the 3IL state. We also summarize the properties of PtII bis(acetylide) complexes that show broadband absorption and reverse saturate absorption for application in nonlinear optics. Singlet and triplet energy transfer and localization of the triplet excited state in multiple‐chromophore complexes are also discussed.
Effect of Magnesium on the Solubility of Hydroxyapatite
Authors: Liu Quan , Chen Zhuofan , Pan Haobo , Darvell Brian W. , Matinlinna Jukka Pekka
Published: November 2016

As an abundant cation in the human body, magnesium plays important roles in physiological and pathological processes. In particular, magnesium deficiency is associated with osteoporosis. Hence, Mg may be involved in the biodegradation and reconstruction of bone mineral. Previously, Mg‐containing hydroxyapatite (HAp) has been synthesized as a model for bone mineral, and its properties, such as crystal size and crystallinity, have been examined. However, the effect of solution magnesium on the effective solubility of hydroxyapatite has not been studied in detail. Here, for a series of magnesium concentrations in the background solution, the mass solubility of hydroxyapatite was determined through the solid titration method at pH 3–5 and 37 °C. A general, quasilogarithmic increase in solubility was found with increasing magnesium concentration. Whether this is due to nucleation inhibition or solution complexation has yet to be ascertained, although the latter is likely on simple chemical grounds. As the direct effect of magnesium was to increase the solubility of HAp in a concentration‐dependent manner, this cannot be the direct cause of osteoporosis in the event of magnesium deficiency.
Cyclometalated IrIII Complexes as Mitochondria‐Targeted Photodynamic Anticancer Agents
Authors: Ouyang Miao , Zeng Leli , Qiu Kangqiang , Chen Yu , Ji Liangnian , Chao Hui
Published: November 2016

Photodynamic therapy (PDT) is an attractive therapeutic modality with high therapeutic efficacy and less side effects compared with other therapies. Herein, we developed a series of cyclometalated IrIII complexes based on 2,2′‐biimidazole with different alkyl substitutions (methyl, ethyl, propyl, and butyl). These complexes can efficiently produce singlet oxygen upon light irradiation. In vitro photocytotoxicity towards four cell lines (HeLa, A549, A549R, and LO2) was examined. Ir1–Ir5 show quick penetration of cells, remarkable mitochondrial accumulation, strong phototoxicity, and they exhibit high selectivity between tumor cells and normal cells. With the highest 1O2 quantum yields, Ir5 presents the best PDT efficiency with a high phototoxicity index (PI) value (PI = 150) towards HeLa cells. This work provides a valuable avenue to improve the PDT effect by tuning the lipophilicity and other properties with variation of the alkyl substitution on the photosensitizer. In addition, their satisfying PDT effect to a cisplatin‐resistant cell line (A549R) may contribute to the future development of improved chemotherapeutics.
Trinuclear Complexes Derived from R/S Schiff Bases – Chiral Single‐Molecule Magnets
Authors: Escuer Albert , Mayans Julia , Font‐Bardia Merce , Di Bari Lorenzo , Górecki Marcin
Published: November 2016

The employment of enantiomerically pure Schiff bases in manganese chemistry is revealed to be an excellent method to obtain chiral single‐molecule magnets and has allowed the characterization of several pairs of enantiomers, for which the magnetic properties were investigated. The reported systems consist of MnIII–MnII–MnIII linear trimers or MnIII3 cations in a triangular arrangement including the first example of a µ3‐Cl bridge in an isolated manganese triangle.
Metal‐Containing Pharmacophores in Molecularly Targeted Anticancer Therapies and Diagnostics
Authors: Yang Mu , Bierbach Ulrich
Published: November 2016

Molecularly targeted therapeutic agents make up an important class of oncology drugs that are used either alone, or in combination with classical cytotoxic agents, to combat many solid tumors and hematological cancers. Their targets in cancer cells are proteins that are encoded by oncogenes, which regulate cell growth, survival, and proliferation. These include a number of signal‐transducing and angiogenesis‐related kinases, hormone receptors, and certain cell‐surface antigens. Targeting of cancer cells harboring oncogenic molecular targets with precision medicines, while sparing the vast majority of normal healthy cells, has led to promising new treatments for cancer patients. Molecularly targeted therapeutic agents promise higher efficacy and weaker side effects than the traditional cytotoxic chemotherapies. Simple metal complexes and metal–organic hybrid agents have been the subjects of investigation for many years since the success of cisplatin in treating genitourinary cancers, but their applications in targeted therapies remain underexplored. In this review we highlight the development of metal‐based targeted cancer therapeutic agents with unique structures and functions. These strategies provide exciting opportunities for discovering new therapeutic and diagnostic agents for clinical uses.
Efficient Electrosynthesis of AgIISO4: A Powerful Oxidizer and Narrow Band Gap Semiconductor
Authors: Połczyński Piotr , Gilewski Tomasz E. , Gawraczyński Jakub , Derzsi Mariana , Leszczyński Piotr Jerzy , Gadomski Wojciech , Mazej Zoran , Jurczakowski Rafał , Grochala Wojciech
Published: November 2016

A novel and efficient method for the synthesis of antiferromagnetic silver(II) sulfate, AgIISO4, on a 20 g scale on the basis of electrosynthesis at highly anodic potentials of AgIHSO4 solutions in 96 % sulfuric acid is reported. The product does not form at the electrode surface but rather precipitates from a saturated solution of Ag(HSO4)2 in H2SO4, and compact crystallites up to 250 µm in length are formed. The yield of electrolysis reaches 75 %. The remaining H2SO4 that wets the crystals of AgSO4 is rinsed off by using anhydrous HF to yield a dry product free from crystalline or amorphous impurities, unlike previous synthetic methods. Impedance spectroscopy measurements indicate that AgSO4 is a narrow band gap semiconductor with an activation energy for conductivity of about 1.0 eV at –50 °C, which is comparable to that of elemental silicon. Theoretical hybrid density functional theory calculations corroborate this result, which yield a 0.90–0.97 eV (indirect–direct) band gap at the Fermi level (at 0 K).
Effect of Pyridyl Substitution on Chemical and Photochemical Water Oxidation by [Ru(terpyridine)(bipyridine)(OH2)]2+ Scaffolds
Authors: Patel Jully , Majee Karunamay , Ahmad Ejaz , Das Babulal , Padhi Sumanta Kumar
Published: November 2016

The complexes [Ru(2‐py‐tpy)(bpy)(OH2)][PF6]2 (1; bpy = 2,2′‐bipyridine), [Ru(3‐py‐tpy)(bpy)(OH2)][PF6]2 (2), and [Ru(4‐py‐tpy)(bpy)(OH2)][PF6]2 (3; n‐py‐tpy = 4′‐(n‐pyridyl)‐2,2′:6′,2′′‐terpyridine, n = 2–4), as electronic modifications of the [Ru(tpy)(bpy)(OH2)][PF6]2 scaffold, have been synthesized and characterized thoroughly by several spectroscopic methods. All three complexes were employed as catalysts for chemical and photochemical water oxidation. The free nitrogen atom of the pyridine ring in catalysts 1–3 is protonated at pH 1 and acts as an electron‐withdrawing group. For 2, the meta‐nitrogen atom has a larger withdrawing effect compared with those of 1 and 3, as the positive charge (δ+) is delocalized only at the carbon atoms. However, the positive charge (δ+) is distributed among the nitrogen and carbon atoms of the pyridine ring for the ortho‐ and para‐nitrogen atoms in 1 and 3, respectively. Electrochemical and manometry studies revealed that 1 and 3 are better catalysts owing to the weaker electron‐withdrawing effects than that for 2. All of these complexes also act as efficient catalysts towards the photo‐oxidation of water in pH 6.5 phosphate buffer at 20 °C in the presence of [Ru(bpy)3]2+ as a photosensitizer and Na2S2O8 as a sacrificial electron acceptor.
Isomeric Effect on the Pharmacokinetic Behavior of Anticancer CuII Mixed Chelate Complexes: Experimental and Theoretical Approach
Authors: García‐Ramos Juan Carlos , Vértiz‐Serrano Guadalupe , Macías‐Rosales Lucia , Galindo‐Murillo Rodrigo , Toledano‐Magaña Yanis , Bernal Juan Pablo , Cortés‐Guzmán Fernando , Ruiz‐Azuara Lena
Published: November 2016

We present herein the results of a pharmacokinetic (PK) study of CuII mixed‐chelate coordination compound CasIII‐La {[Cu(5,6‐dimethyl‐1,10‐phenanthroline)(acetylacetonate)(H2O)]NO3}, which belongs to the antineoplastic family of compounds known as Casiopeínas. The main interest in this molecule lies in the big difference in its lethal dose and PK parameters in Wistar rats compared with its structural isomer CasIII‐Ea {[Cu(4,7‐dimethyl‐1,10‐phenanthroline)(acetylacetonate)(H2O)]NO3}. For instance, the half‐lives of these compounds are 9.6 ± 1.15 and 48 ± 4.6 h for CasIII‐La and CasIII‐Ea, respectively. The differences in the half‐lives have been attributed to their different capacities to cross cellular membranes. Molecular dynamics studies of a fraction of a cell membrane and Casiopeínas were developed to identify the possible intermolecular interactions responsible for the retention of the compound inside the cellular membrane. Also, quantum theory of atoms‐in‐molecules studies was developed to determine the capacity of the hydrogen atoms of methyl groups to participate in intermolecular interactions. In addition, peripheral human blood lymphocyte and macrophage samples were used to determine the cross‐membrane effect on cytotoxicity.
Base‐Free Transfer Hydrogenation with an Ionic‐Liquid‐Supported Ruthenium η6‐Arene Bis(pyrazolyl)methane Catalyst
Authors: Sepúlveda Francisco , Carrión M. Carmen , Phillips Andrew D. , Jalón Félix A. , Dyson Paul J. , Manzano Blanca R.
Published: November 2016

Ruthenium complexes of the type [RuCl(η6‐arene)(NN)]X (X = BF4 or BPh4) featuring an η6‐arene ligand modified with an imidazolium ring and incorporating the bis(azo) chelating (NN) ligands 2‐hydroxyphenylbis(3,5‐dimethylpyrazol‐1‐yl)methane or 2‐nitrophenylbis(3,5‐dimethylpyrazol‐1‐yl)methane are reported. The catalytic activities of the complexes were evaluated in the transfer hydrogenation of benzaldehyde to benzyl alcohol with iPrOH as the hydrogen donor in the absence of a base and under biphasic conditions; one of the two phases was iPrOH, and the other was an ionic liquid. The catalysts featuring the imidazolium‐modified η6‐arene could be recycled and reused with only a minor decrease in substrate conversion after multiple reaction cycles. The reaction rate was strongly influenced by the type of ionic liquid employed in the biphasic system.
Synthesis of Cyclopentadienyl‐Based Tricarbonyl Rhenium Complexes and Some Unusual Reactivities of Cyclopentadienyl Substituents
Authors: Raju Suresh , van Slagmaat Christian A. M. R. , Lutz Martin , Kleijn Hendrik , Jastrzebski Johann T. B. H. , Moret Marc‐Etienne , Klein Gebbink Robertus J. M.
Published: November 2016

Cyclopentadienyl‐based (Cp‐based) tricarbonyl rhenium complexes [Cp′Re(CO)3] are convenient precursors for the corresponding Cp‐based trioxorhenium complexes (Cp′ReO3), which are potential catalysts for the deoxydehydration (DODH) of diols to olefins. To evaluate the influence of different Cp substituents in Cp′ReO3 complexes in DODH, a series of alkyl‐substituted Cp′Re(CO)3 complexes (1a–8a) were synthesized. High yields (86–98 %) were obtained from the reactions of Re2(CO)10 with the corresponding Cp′H ligands (1–8). The C–O infrared absorptions of 1a–8a indicate that the electron‐donating character of the Cp ligand increases with the number of substituents attached directly to the Cp ring. Analogous aryl‐substituted complexes 10a–12a containing bulky phenyl groups were accessed through the salt metathesis of ReBr(CO)5 with the lithium salt of the deprotonated ligand (Cp′Li), and the aryl groups decreased the electron donation. Furthermore, an unusual [6+4] cycloaddition reaction of (CpMe4H)Re(CO)3 (8a) with excess ligand resulted in the highly asymmetric Cp′Re(CO)3 complex 9a. Finally, the reaction of the tetraphenylcyclopentadienone ligand with Re2(CO)10 was investigated and led to the isolation of two unusual compounds, namely, Re(CO)3 complexes of the Shvo‐type hydroxytetraphenylcyclopentadienyl ligand, [Ph4Cp(OH)]Re(CO)3 (13a), and a benzofuran‐fused cyclopentadienyl ligand, [Ph3Cp(C6H4O)]Re(CO)3 (14a). X‐ray crystal structures were obtained for the new Cp′Re(CO)3 complexes (CptBu2H3)Re(CO)3 (2a), [1,2,3‐Me3(tetrahydroindenyl)]Re(CO)3 (7a), 9a, 13a, and 14a, which all have the typical three‐legged “piano‐stool” configuration.
A Ru(bipyridine)3[PF6]2 Complex with a Rhodamine Unit – Synthesis, Photophysical Properties, and Application in Acid‐Controllable Triplet–Triplet Annihilation Upconversion
Authors: Cui Xiaoneng , Zhao Jianzhang , Karatay Ahmet , Yaglioglu Halime Gul , Hayvali Mustafa , Küçüköz Betül
Published: November 2016

Invited for the cover of this issue are the groups of Jianzhang Zhao from Dalian University of Technology, China, and Mustafa Hayvali from Ankara University, Turkey. The cover image shows switching of the 3MLCT states of a ruthenium(II) complex by rhodamine.
Facile Synthesis of Polycyclic Aromatic Hydrocarbons: Brønsted Acid Catalyzed Dehydrative Cycloaromatization of Carbonyl Compounds in 1,1,1,3,3,3‐Hexafluoropropan‐2‐ol
Authors: Fujita Takeshi , Takahashi Ikko , Hayashi Masaki , Wang Jingchen , Fuchibe Kohei , Ichikawa Junji
Published: November 2016

The cycloaromatization of aromatic aldehydes and ketones was readily achieved by using a Brønsted acid catalyst in 1,1,1,3,3,3‐hexafluoropropan‐2‐ol (HFIP). In the presence of a catalytic amount of trifluoromethanesulfonic acid, biaryl‐2‐ylacetaldehydes and 2‐benzylbenzaldehydes underwent sequential intramolecular cationic cyclization and dehydration to afford phenacenes and acenes, respectively. Furthermore, biaryl‐2‐ylacetaldehydes bearing a cyclopentene moiety at the α‐position underwent unprecedented cycloaromatization including ring expansion to afford triphenylenes. HFIP effectively promoted the cyclizations by suppressing side reactions presumably as a result of stabilization of the cationic intermediates.
Numerical study of the faithful replication of micro/nanostructures on curved surfaces by the electrohydrodynamic instability process
Authors: Li Hefu , Yu Weixing , Wang Taisheng , Liu Zhenyu , Desmulliez M. P. Y.
Published: November 2016

This paper reports the numerical study of the one‐step faithful replication of micro/nano‐scale structures on a fiber surface by using the electrohydrodynamic instability patterning (EHDIP) process. By employing a rigorous numerical analysis method, conditions are revealed under which the faithful replication of a pattern can be achieved from a curved master electrode. It is found that the radius of curvature of the fiber plays an important role in determining the final morphology of the pattern when the destabilizing electric field is dominant in both the flat and patterned template cases. In general, stronger electric fields and larger radii of curvature of the substrate are favorable for the faithful replication of the pattern. In addition, theoretical analysis shows that higher aspect ratio of micro/nanostructures can be obtained on curved surfaces by using a master with a much lower aspect ratio. The results demonstrated in this study aims to provide guidelines for the faithful fabrication of micro/nanostructures on curved surfaces by the EHDIP process.