bluuebunny/crossref_metadata_2025 huggingface dataset:
Proof of Principle: Immobilisation of Robust CuII3TbIII‐Macrocycles on Small, Suitably Pre‐functionalised Gold Nanoparticles
Authors: Feltham Humphrey L. C. , Dumas Christophe , Mannini Matteo , Otero Edwige , Sainctavit Philippe , Sessoli Roberta , Meledandri Carla J. , Brooker Sally
Published: December 2016

Invited for the front cover of this issue is the multi‐national collaborative team of Carla Meledandri, Roberta Sessoli, Sally Brooker and co‐workers at the Universities of Otago and Florence along with IMPMC and SOLEIL. The image depicts the binding of huge amounts of macrocyclic complexes onto small monodisperse gold nanoparticles prefunctionalised by carboxylate tethers. Read the full text of the article at 10.1002/chem.201604821.
A Ring‐Opening Metathesis Polymerization Catalyst That Exhibits Redox‐Switchable Monomer Selectivities
Authors: Lastovickova Dominika N. , Shao Huiling , Lu Gang , Liu Peng , Bielawski Christopher W.
Published: December 2016

A ring‐opening metathesis polymerization catalyst supported by a redox‐active N‐heterocyclic carbene was synthesized and found to undergo reversible reduction. In its neutral form, the catalyst polymerized 1,5‐cis,cis‐cyclooctadiene at a higher rate than that of a norbornene derivative; however, upon reduction, the selectivity was found to reverse. Utilizing this oxidation state dependent selectivity, a series of copolymers with controlled compositions, microstructures, and physical properties were prepared by redox‐switching the catalyst over the course of a series of polymerization reactions.
Sonofragmentation of Ionic Crystals
Authors: Kim Hyo Na , Suslick Kenneth S.
Published: December 2016

Mechanochemistry deals with the interface between the chemical and the mechanical worlds and explores the physical and chemical changes in materials caused by an input of mechanical energy. As such, the chemical and physical effects of ultrasound, i.e., sonochemistry, are forms of mechanochemistry. In this paper, the fragmentation of ionic crystals during ultrasonic irradiation of slurries has been quantitatively investigated: the rate of fragmentation depends strongly on the strength of the materials (as measured by Vickers hardness or by Young's modulus). This is a mechanochemical extension of the Bell–Evans–Polanyi Principle or Hammond's Postulate: activation energies for solid fracture correlate with binding energies of solids. Sonofragmentation is unaffected by slurry loading or liquid vapor pressure, but is suppressed by increasing liquid viscosity. The mechanism of the particle breakage is consistent with a direct interaction between the shockwaves created by the ultrasound (through acoustic cavitation) and the solid particles in the slurry. Fragmentation is proposed to occur from defects in the solids induced by compression–expansion, bending, or torsional distortions of the crystals.
Modeling Milk Heating Processes for the Production of Milk Shelf‐stable without Refrigeration
Authors: Stoeckel Marina , Lidolt Melanie , Hinrichs Jörg
Published: December 2016

Modeling milk heating processes leading to milk shelf‐stable without refrigeration was studied. Evaluated criteria were: inactivation of bacterial spores and highly thermosresistant spores (HTRS), reduction of the plasmin activity and Pseudomonas peptidases, lactulose formation, browning, and thiamin loss. Special emphasis was laid on including the inactivation of milk spoilage enzymes in the modeling approach. The reduction of bacterial spores and plasmin activity was shown to be essential for the shelf‐stability. Using modeling, risks posed by the selected criteria can be identified and eliminated by adapting the processes.
Selenophenes: Introducing a New Element into the Core of Non‐Steroidal Estrogen Receptor Ligands
Authors: Zhang Silong , Wang Zhiyong , Hu Zhiye , Li Changhao , Tang Chu , Carlson Kathryn E. , Luo Junjie , Dong Chune , Katzenellenbogen John A. , Huang Jian , Zhou Hai‐Bing
Published: December 2016

The importance of the heterocyclic core elements with peripheral phenolic and alkyl substituents as a dominant structural motif of ligands for the estrogen receptor (ER) has been well recognized. In this study we expanded the structural diversity of core elements by preparing selenium‐containing heterocycles and exploring the activities of these selenophenes on the two ERs, ERα and ERβ. Careful structure–activity relationship (SAR) analysis of their ER binding affinities showed that most selenophenes are ERβ‐selective, with the position of the phenol substituents on the selenophene core and the nature of these substituents having a marked effect on their binding affinities. The compound bis(2‐fluoro‐4‐hydroxyphenyl)selenophene (2 f) has the highest relative binding affinity (RBA) of 24.3 for ERβ. In transcription assays, most selenophenes were found to exhibit partial to full agonist activity for both ER subtypes, with compounds bis(2‐methyl‐4‐hydroxyphenyl)selenophene (2 b), bis(4‐fluoro‐3‐hydroxyphenyl)3‐bromoselenophene (6 f), and 2,3,5‐tris(hydroxyphenyl)thiophenes (8 b and 8 d) profiling as superagonists for ERα; however, several compounds display a range of ERα or ERβ antagonistic activities. A few selenophenes exhibited antiproliferative activity, with compound 8 c showing antiproliferative effects similar to that of 4‐hydroxytamoxifen in breast cancer MCF‐7 cells while being nontoxic to normal VERO cells. These new ligands could act as models for the development of novel agents leading to improved therapeutics that target the estrogen receptor.
A multi‐institutional analysis of peritransplantation radiotherapy in patients with relapsed/refractory Hodgkin lymphoma undergoing autologous stem cell transplantation
Authors: Milgrom Sarah A. , Jauhari Shekeab , Plastaras John P. , Nieto Yago , Dabaja Bouthaina S. , Pinnix Chelsea C. , Smith Grace L. , Allen Pamela K. , Lukens J. Nicholas , Maity Amit , Oki Yasuhiro , Fanale Michelle A. , Nasta Sunita D.
Published: December 2016

BACKGROUND

No consensus exists regarding the use of radiotherapy (RT) in conjunction with high‐dose chemotherapy and autologous stem cell transplantation (HDC/ASCT) for patients with relapsed/refractory classical Hodgkin lymphoma (HL). The objectives of the current study were to characterize practice patterns and assess the efficacy and toxicity of RT at 2 major transplantation centers.

METHODS

Eligible patients underwent HDC/ASCT from 2006 through 2015 using the combination of either carmustine (BCNU), etoposide, cytarabine, and melphalan (BEAM) or cyclophosphamide, BCNU, and etoposide (CBV).

RESULTS

For the cohort of 189 patients, the 4‐year overall survival rate was 80%, the progression‐free survival rate was 67%, and the local control (LC) rate was 68%. RT was used within 4 months of ASCT for 22 patients (12%) and was given more often for disease that was early stage, primary refractory, or [18F]fluorodeoxyglucose (FDG)‐avid at the time of HDC/ASCT. Disease recurrence occurring after HDC/ASCT was associated with primary refractory disease and FDG‐avidity at the time of HDC/ASCT. RT was not found to be associated with LC, progression‐free survival, or overall survival on univariate analysis. In a model incorporating primary refractory HL and FDG‐avid disease at the time of HDC/ASCT, RT was found to be associated with a decreased risk of local disease recurrence (hazard ratio, 0.3; P = .02). In patients with primary refractory HL and/or FDG‐avid disease at the time of HDC/ASCT, the 4‐year LC rate was 81% with RT versus 49% without RT (P = .03). There was one case of Common Terminology Criteria for Adverse Events grade ≥ 3 RT‐related toxicity (acute grade 3 pancytopenia).

CONCLUSIONS

In patients undergoing ASCT for relapsed/refractory HL, peritransplantation RT was used more often for disease that was early stage, primary refractory, or FDG‐avid after salvage conventional‐dose chemotherapy. RT was associated with improved LC of high‐risk localized disease and was well tolerated with modern techniques. Cancer 2017;123:1363–1371. © 2016 American Cancer Society.
The known unknown
Authors: Khuri Fadlo R.
Published: December 2016

Cancer care and its application have differed for some time between the developed and the developing nations. These differences are likely to deepen with the onset of high‐impact, high‐cost molecular diagnostics, immunotherapy, and targeted therapy.
Mid‐life environmental enrichment increases synaptic density in CA1 in a mouse model of Aβ‐associated pathology and positively influences synaptic and cognitive health in healthy ageing
Authors: Stuart Kimberley E. , King Anna E. , Fernandez‐Martos Carmen M. , Dittmann Justin , Summers Mathew J. , Vickers James C.
Published: December 2016

Early‐life cognitive enrichment may reduce the risk of experiencing cognitive deterioration and dementia in later‐life. However, an intervention to prevent or delay dementia is likely to be taken up in mid to later‐life. Hence, we investigated the effects of environmental enrichment in wildtype mice and in a mouse model of Aβ neuropathology (APPSWE/PS1dE9) from 6 months of age. After 6 months of housing in standard laboratory cages, APPSWE/PS1dE9 (n = 27) and healthy wildtype (n = 21) mice were randomly assigned to either enriched or standard housing. At 12 months of age, wildtype mice showed altered synaptic protein levels and relatively superior cognitive performance afforded by environmental enrichment. Environmental enrichment was not associated with alterations to Aβ plaque pathology in the neocortex or hippocampus of APPSWE/PS1dE9 mice. However, a significant increase in synaptophysin immunolabeled puncta in the hippocampal subregion, CA1, in APPSWE/PS1dE9 mice was detected, with no significant synaptic density changes observed in CA3, or the Fr2 region of the prefrontal cortex. Moreover, a significant increase in hippocampal BDNF was detected in APPSWE/PS1dE9 mice exposed to EE, however, no changes were detected in neocortex or between Wt animals. These results demonstrate that mid to later‐life cognitive enrichment has the potential to promote synaptic and cognitive health in ageing, and to enhance compensatory capacity for synaptic connectivity in pathological ageing associated with Aβ deposition.
Multifunctional Photonic Molecular Logic Gate Based On A Biphotochromic Dyad With Reduced Energy Transfer
Authors: Budyka Mikhail F. , Li Vitalii M.
Published: December 2016

Using molecular logic gates (MLGs) for information processing attracts attention due to perspectives of creating molecular computers. Biphotochromic dyads are suitable models of photonic MLGs. However, they suffer from one weakness: the activity of one of the photochromes is often quenched because of Förster resonance energy transfer (FRET). Herein, we designed a dyad with reduced FRET, in which both photochromes keep their photoactivity thanks to spectral and spatial separation, allowing MLG switching between different states. This novel dyad reproduces the functionality of the full set of 16 two‐input gates, as well a reversible gate–dual inverter, all gates are photonic.
From 1,4‐Phenylenebis(phenylmaleate) to a Room‐Temperature Liquid‐Crystalline Benzo[ghi]perylene Diimide
Authors: Belarmino Cabral Marília Gabriela , Pereira de Oliveira Santos Deise Maria , Cristiano Rodrigo , Gallardo Hugo , Bentaleb Ahmed , Hillard Elizabeth A. , Durola Fabien , Bock Harald
Published: December 2016

The photocyclization of tetraethyl 1,4‐phenylenebis(phenylmaleate) in the presence of iodine and oxygen predominantly yields tetraethyl [5]helicene‐5,6,9,10‐tetracarboxylate, together with small amounts of tetraethyl dibenz[a,h]anthracene‐5,6,12,13‐tetracarboxylate and tetraethyl benzo[ghi]perylene‐3,4,11,12‐tetracarboxylate. The helicene tetraester is planarized to the benzoperylene tetraester by Scholl reaction with AlCl3 followed by reesterification of the partially hydrolyzed crude product. Subsequent treatment with a branched alkylamine yields a columnar liquid‐crystalline benzoperylene diimide whose mesophase is stable at room temperature despite its limited and non‐centrosymmetric alkyl periphery. Its absorption spectrum is markedly red‐shifted compared to that of a similar benzoperylene triimide.
Patient Perceptions of Care as Influenced by a Large Institutional Pharmacogenomic Implementation Program
Authors: McKillip RP , Borden BA , Galecki P , Ham SA , Patrick‐Miller L , Hall JP , Hussain S , Danahey K , Siegler M , Sorrentino MJ , Sacro Y , Davis AM , Rubin DT , Lipstreuer K , Polonsky TS , Nanda R , Harper WR , Koyner JL , Burnet DL , Stadler WM , Ratain MJ , Meltzer DO , O'Donnell PH
Published: December 2016

Despite growing clinical use of genomic information, patient perceptions of genomic‐based care are poorly understood. We prospectively studied patient‐physician pairs who participated in an institutional pharmacogenomic implementation program. Trust/privacy/empathy/medical decision‐making (MDM)/personalized care dimensions were assessed through patient surveys after clinic visits at which physicians had access to preemptive pharmacogenomic results (Likert scale, 1 = minimum/5 = maximum; mean [SD]). From 2012–2015, 1,261 surveys were issued to 507 patients, with 792 (62.8%) returned. Privacy, empathy, MDM, and personalized care scores were significantly higher after visits when physicians considered pharmacogenomic results. Importantly, personalized care scores were significantly higher after physicians used pharmacogenomic information to guide medication changes (4.0 [1.4] vs. 3.0 [1.6]; P < 0.001) compared with prescribing visits without genomic guidance. Multivariable modeling controlling for clinical factors confirmed personalized care scores were more favorable after visits with genomic‐influenced prescribing (odds ratio [OR] = 3.26; 95% confidence interval [CI] = (1.31–8.14); P < 0.05). Physicians seem to individualize care when utilizing pharmacogenomic results and this decision‐making augmentation is perceived positively by patients.
Comparison of Outcomes Following a Switch From a Brand to an Authorized Versus Independent Generic Drug
Authors: Hansen RA , Qian J , Berg RL , Linneman JG , Seoane‐Vazquez E , Dutcher S , Raofi S , Page CD , Peissig PL
Published: December 2016

Authorized generics are identical in formulation to brand drugs, manufactured by the brand company but marketed as a generic. Generics, marketed by generic manufacturers, are required to demonstrate pharmaceutical and bioequivalence to the brand drug, but repetition of clinical trials is not required. This retrospective cohort study compared outcomes for generics and authorized generics, which serves as a generic vs. brand proxy that minimizes bias against generics. For the seven drugs studied between 1999 and 2014, 5,234 unique patients were on brand drugs prior to generic entry and 4,900 (93.6%) switched to a generic. During the 12 months following the brand‐to‐generic switch, patients using generics vs. authorized generics were similar in terms of outpatient visits, urgent care visits, hospitalizations, and medication discontinuation. The likelihood of emergency department (ED) visits was slightly higher for authorized generics compared with generics. These data suggest that generics were clinically no worse than their proxy brand comparators.
Carbonate Ions Induce Highly Efficient Electrocatalytic Water Oxidation by Cobalt Oxyhydroxide Nanoparticles
Authors: Aiso Kaoru , Takeuchi Ryouchi , Masaki Takeshi , Chandra Debraj , Saito Kenji , Yui Tatsuto , Yagi Masayuki
Published: December 2016

Synthetic models of oxygen evolving complex (OEC) are used not only to gain better understanding of the mechanism and the roles of cofactors for water oxidation in photosynthesis, but also as water oxidation catalysts to realize artificial photosynthesis, which is anticipated as a promising solar fuel production system. However, although much attention has been paid to the composition and structure of active sites for development of heterogeneous OEC models, the cofactors, which are essential for water oxidation by the photosynthetic OEC, remain little studied. The high activity of CoO(OH) nanoparticles for electrocatalytic water oxidation is shown to be induced by a CO32− cofactor. The possibility of CO32− ions acting as proton acceptors for O−O bond formation based on the proton‐concerted oxygen atom transfer mechanism is proposed. The O−O bond formation is supposed to be accelerated due to effective proton acceptance by adjacent CO32− ions coordinated on the CoIV center in the intermediate, which is consistent with Michaelis–Menten‐type kinetics and the significant H/D isotope effect observed in electrocatalysis.
Sunlight‐Dependent Hydrogen Production by Photosensitizer/Hydrogenase Systems
Authors: Adam David , Bösche Lisa , Castañeda‐Losada Leonardo , Winkler Martin , Apfel Ulf‐Peter , Happe Thomas
Published: December 2016

We report a sustainable in vitro system for enzyme‐based photohydrogen production. The [FeFe]‐hydrogenase HydA1 from Chlamydomonas reinhardtii was tested for photohydrogen production as a proton‐reducing catalyst in combination with eight different photosensitizers. Using the organic dye 5‐carboxyeosin as a photosensitizer and plant‐type ferredoxin PetF as an electron mediator, HydA1 achieves the highest light‐driven turnover number (TONHydA1) yet reported for an enzyme‐based in vitro system (2.9×106 mol(H2) mol(cat)−1) and a maximum turnover frequency (TOFHydA1) of 550 mol(H2) mol(HydA1)−1 s−1. The system is fueled very effectively by ambient daylight and can be further simplified by using 5‐carboxyeosin and HydA1 as a two‐component photosensitizer/biocatalyst system without an additional redox mediator.
Making the cut: Innovative methods for optimizing perfusion‐based migration assays
Authors: Holt Andrew W. , Howard William E. , Ables Elizabeth T. , George Stephanie M. , Kukoly Cindy A. , Rabidou Jake E. , Francisco Jake T. , Chukwu Angel N. , Tulis David A.
Published: December 2016

Application of fluid shear stress to adherent cells dramatically influences their cytoskeletal makeup and differentially regulates their migratory phenotype. Because cytoskeletal rearrangements are necessary for cell motility and migration, preserving these adaptations under in vitro conditions and in the presence of fluid flow are physiologically essential. With this in mind, parallel plate flow chambers and microchannels are often used to conduct in vitro perfusion experiments. However, both of these systems currently lack capacity to accurately study cell migration in the same location where cells were perfused. The most common perfusion/migration assays involve cell perfusion followed by trypsinization which can compromise adaptive cytoskeletal geometry and lead to misleading phenotypic conclusions. The purpose of this study was to quantitatively highlight some limitations commonly found with currently used cell migration approaches and to introduce two new advances which use additive manufacturing (3D printing) or laser capture microdissection (LCM) technology. The residue‐free 3D printed insert allows accurate cell seeding within defined areas, increases cell yield for downstream analyses, and more closely resembles the reported levels of fluid shear stress calculated with computational fluid dynamics as compared to other residue‐free cell seeding techniques. The LCM approach uses an ultraviolet laser for “touchless technology” to rapidly and accurately introduce a custom‐sized wound area in otherwise inaccessible perfusion microchannels. The wound area introduced by LCM elicits comparable migration characteristics compared to traditional pipette tip‐induced injuries. When used in perfusion experiments, both of these newly characterized tools were effective in yielding similar results yet without the limitations of the traditional modalities. These innovative methods provide valuable tools for exploring mechanisms of clinically important aspects of cell migration fundamental to the pathogenesis of many flow‐mediated disorders and are applicable to other perfusion‐based models where migration is of central importance. © 2016 International Society for Advancement of Cytometry
Achondroplasia: Development, pathogenesis, and therapy
Authors: Ornitz David M. , Legeai‐Mallet Laurence
Published: December 2016

Autosomal dominant mutations in fibroblast growth factor receptor 3 (FGFR3) cause achondroplasia (Ach), the most common form of dwarfism in humans, and related chondrodysplasia syndromes that include hypochondroplasia (Hch), severe achondroplasia with developmental delay and acanthosis nigricans (SADDAN), and thanatophoric dysplasia (TD). FGFR3 is expressed in chondrocytes and mature osteoblasts where it functions to regulate bone growth. Analysis of the mutations in FGFR3 revealed increased signaling through a combination of mechanisms that include stabilization of the receptor, enhanced dimerization, and enhanced tyrosine kinase activity. Paradoxically, increased FGFR3 signaling profoundly suppresses proliferation and maturation of growth plate chondrocytes resulting in decreased growth plate size, reduced trabecular bone volume, and resulting decreased bone elongation. In this review, we discuss the molecular mechanisms that regulate growth plate chondrocytes, the pathogenesis of Ach, and therapeutic approaches that are being evaluated to improve endochondral bone growth in people with Ach and related conditions. Developmental Dynamics 246:291–309, 2017. © 2016 Wiley Periodicals, Inc.
Do settlement dynamics influence competitive interactions between an alien tunicate and its native congener?
Authors: Bouchemousse Sarah , Lévêque Laurent , Viard Frédérique
Published: December 2016

Variation in density of early stages, that is, larvae and juveniles, is a major determinant of the distribution and abundance of the adult population of most marine invertebrates. These early stages thus play a key role in competitive interactions, and, more specifically, in invasion dynamics when biologically similar native and non‐native species (NNS) come into contact in the same habitat. We examined the settlement dynamics and settlement rate of two important members of the fouling community that are common on human‐made infrastructures around the world: Ciona robusta (formerly known as Ciona intestinalis type A) and C. intestinalis (formerly known as C. intestinalis type B). In the western English Channel, the two species live in close syntopy following the recent introduction of C. robusta in the native European range of C. intestinalis. Using settlement panels replaced monthly over 2 years in four marinas (including one studied over 4 years) and species‐diagnostic molecular markers to distinguish between juveniles of both species (N = 1,650), we documented similar settlement dynamics of both species, with two settlement periods within a calendar year. With one exception, settlement times were highly similar in the congeners. Although the NNS showed lower settlement density than that of the native congener, its juvenile recruitment was high during the second settlement period that occurs after the warm season, a pattern also observed in adult populations. Altogether, our results suggest that species’ settlement dynamics do not lead to the dominance of one species over the other through space monopolization. In addition, we showed that changes over time are more pronounced in the NNS than in the native species. This is possibly due to a higher sensitivity of the NNS to changes of environmental factors such as temperature and salinity. Environmental changes may thus eventually modify the strength of competitive interactions between the two species as well as species dominance.
Detrending phenological time series improves climate–phenology analyses and reveals evidence of plasticity
Authors: Iler Amy M. , Inouye David W. , Schmidt Niels M. , Høye Toke T.
Published: December 2016

Time series have played a critical role in documenting how phenology responds to climate change. However, regressing phenological responses against climatic predictors involves the risk of finding potentially spurious climate–phenology relationships simply because both variables also change across years. Detrending by year is a way to address this issue. Additionally, detrending isolates interannual variation in phenology and climate, so that detrended climate–phenology relationships can represent statistical evidence of phenotypic plasticity. Using two flowering phenology time series from Colorado, USA and Greenland, we detrend flowering date and two climate predictors known to be important in these ecosystems: temperature and snowmelt date. In Colorado, all climate–phenology relationships persist after detrending. In Greenland, 75% of the temperature–phenology relationships disappear after detrending (three of four species). At both sites, the relationships that persist after detrending suggest that plasticity is a major component of sensitivity of flowering phenology to climate. Finally, simulations that created different strengths of correlations among year, climate, and phenology provide broader support for our two empirical case studies. This study highlights the utility of detrending to determine whether phenology is related to a climate variable in observational data sets. Applying this as a best practice will increase our understanding of phenological responses to climatic variation and change.
Community assembly and the functioning of ecosystems: how metacommunity processes alter ecosystems attributes
Authors: Leibold Mathew A. , Chase Jonathan M. , Ernest S. K. Morgan
Published: December 2016

Recent work linking community structure and ecosystem function has primarily focused on the effects of local species richness but has neglected the dispersal‐dependent processes of community assembly that are ultimately involved in determining community structure and its relation to ecosystems. Here we combine simple consumer‐resource competition models and metacommunity theory with discussion of case studies to outline how spatial processes within metacommunities can alter community assembly and modify expectations about how species diversity and composition influence ecosystem attributes at local scales. We argue that when community assembly is strongly limited by dispersal, this can constrain ecosystem functioning by reducing positive selection effects (reducing the probability of the most productive species becoming dominant) even though it may often also enhance complementarity (favoring combinations of species that enhance production even though they may not individually be most productive). Conversely, excess dispersal with strong source‐sink relations among heterogeneous habitats can reduce ecosystem functioning by swamping local filters that would normally favor better‐suited species. Ecosystem function is thus most likely maximized at intermediate levels of dispersal where both of these effects are minimized. In this scenario, we find that the selection effect is maximized, while complementarity is often reduced and local diversity may often be relatively low. Our synthesis emphasizes that it is the entire set of community assembly processes that affect the functioning of ecosystems, not just the part that determines local species richness.
Do species' strategies and type of stress predict net positive effects in an arid ecosystem?
Authors: Graff Pamela , Aguiar Martin R.
Published: December 2016

A proposed refinement to the stress‐gradient hypothesis requires consideration of the strategies of the interacting species and the characteristics of the stress factors. While the strength and direction of these interactions can be predicted for different ecosystems, this idea remains largely untested in the field. We performed a manipulative field experiment complemented with a descriptive study to test the predictions in a natural setting that represents the extreme end of a precipitation gradient. There, wind driven desiccation and water availability are the main stressors (non‐resource and resource‐based stresses, respectively). We evaluated the interaction between the shrub and grasses that are dominant in the Patagonian steppe. The species had differences in morpho‐functional traits and drought tolerance that fit into the C–S axis of Grime's strategies. We experimentally separated root zones to limit direct competition for soil moisture and reduce the resource‐based stress on grasses. We also manipulated the distance to shrubs to evaluate non‐resource stress amelioration by canopies (e.g., sun and wind) on grasses. Finally, we evaluated the distribution of naturally established C and S grasses in the neighborhood of C and S shrubs to infer process‐pattern relationships. Our growth data coincide to a large degree to the predictions. We found positive effects on the growth of beneficiaries when stress was non‐resource based and when strategies differed (i.e., Cshrub–Sgrass and Sshrub–Cgrass). We also found strong negative effects when the abiotic stress was driven by water, particularly on C grasses. Additionally, shrubs only increased the survival of grasses when strategies differed (i.e., Cshrub–Sgrass and Sshrub–Cgrass). Our manipulative and descriptive study supported previous results that showed that stress‐tolerant species are important for the persistence of competitive species at high stress. While the applicability and generality of these predictions remains to be tested with more field experiments, some ecological factors, such as stress types and species traits, can explain much of the variation in how dominant shrubs and grasses interact in this extreme arid environment. Moreover, this framework could be extended to specifically test the importance of facilitation under different levels of stress.
Short‐ and long‐term effects of habitat fragmentation differ but are predicted by response to the matrix
Authors: Evans Maldwyn J. , Banks Sam C. , Driscoll Don A. , Hicks Andrew J. , Melbourne Brett A. , Davies Kendi F.
Published: December 2016

Habitat loss and fragmentation are major threats to biodiversity and ecosystem processes. Our current understanding of the impacts of habitat loss and fragmentation is based largely on studies that focus on either short‐term or long‐term responses. Short‐term responses are often used to predict long‐term responses and make management decisions. The lack of studies comparing short‐ and long‐term responses to fragmentation means we do not adequately understand when and how well short‐term responses can be extrapolated to predict long‐term responses, and when or why they cannot. To address this gap, we used data from one of the world's longest‐running fragmentation experiments, The Wog Wog Habitat Fragmentation Experiment. Using data for carabid beetles, we found that responses in the long term (more than 22 yr post‐fragmentation ≈22 generations) often contrasted markedly with those in the short term (5 yr post‐fragmentation). The total abundance of all carabids, species richness and the occurrence of six species declined in the short term in the fragments but increased over the long term. The occurrence of three species declined initially and continued to decline, whilst another species was positively affected initially but decreased in the long term. Species’ responses to the matrix that surrounds the fragments strongly predicted both the direction (increase/decline in occurrence) and magnitude of their responses to fragmentation. Additionally, species’ responses to the matrix were somewhat predicted by their preferences for different types of native habitat (open vs. shaded). Our study highlights the degree of the matrix's influence in fragmented landscapes, and how this influence can change over time. We urge caution in using short‐term responses to forecast long‐term responses in cases where the matrix (1) impacts species’ responses to fragmentation (by isolating them, creating new habitat or altering fragment habitat) and (2) is likely to change through time.
Preparation of Exoergic Insulating Composite Material Using Electrostatic Adsorption Model
Authors: FUJII ATSUHIRO , HIROTA SHOU , MURAKAMI YOSHINOBU , MUTO HIROYUKI , KAWASHIMA TOMOHIRO , TAJIRI KUNIHIRO , SHIOTA HIROKI , TSURIMOTO TAKAO , NAGAO MASAYUKI
Published: December 2016

To understand the properties of composite insulating materials, dc breakdown testing and the thermal conductivity measurement of polymethylmethacrylate (PMMA)/aluminum oxide (alumina) composite material created using the electrostatic adsorption method were performed. In the PMMA/alumina sample, which has an alumina as a main particle and a PMMA as an adsorption particle, the dc breakdown strength decreased as the alumina content was increased. It is thought that the increase of the interface between an alumina particle and a PMMA particle leads to a lower dc breakdown strength. The thermal conductivity in PMMA/alumina composite material increased with an increase in the alumina content. From these results, it is suggested that the electrostatic adsorption method can produce the various structures in the material and the insulating materials with various properties such as a higher thermal conductivity and greater tolerable breakdown strength by using a combination of the particle size of the main particle and the adsorption particles.
Multimetallic Gold–Iron Compounds Based on Aurated Ferrocenes
Authors: Meyer Nadine , Schucht Heike , Lehmann Christian W. , Weibert Bernhard , Winter Rainer F. , Mohr Fabian
Published: December 2016

A family of aurated ferrocenes was prepared by a transmetallation reaction using ferroceneboronic acid derivatives. With this method, multimetallic ferrocenyl complexes [FcAu(PPh3)] {Fc = (η5‐C5H4)FeCp} and [(µ‐P‐P)(AuFc)2] {P‐P = dppe, dppf}, as well as 1,1′‐diaurated ferrocenes [Fe(η5‐C5H4AuPPh3)2] and [Fe{(η5‐C5H4Au)}2(µ‐P‐P)] {P‐P = dppe, dppf}, were obtained in high yields as air‐stable orange materials. The compounds were characterised by spectroscopic methods, cyclic voltammetry and single‐crystal X‐ray diffraction. The reactivity of the dinuclear gold(I) complex in oxidative addition reactions is also reported.
Chemoselective Access to π‐Conjugated Heterocycles by Stille and Sonogashira Reactions on 2‐Substituted 4H‐Pyrido[e][1,3]oxazin‐4‐ones
Authors: Le Falher Laetitia , Mumtaz Amara , Nina Diogo Anthony , Thorimbert Serge , Botuha Candice
Published: December 2016

Site‐selective PdII‐catalyzed cross‐coupling reactions of 2‐substituted‐4H‐pyrido[e][1,3]oxazin‐4‐ones were developed. C4‐ and C5‐alkynylated pyridooxazinones were thus obtained through Sonogashira coupling, whereas the efficient incorporation of (hetero)aryl and ethenyl substituents at the C5 position was achieved by Stille coupling. Finally, an example of one‐pot sequential multiple Sonogashira reactions with different alkynes was realized. The strategy developed herein provides rapid access to polyfunctionalized precursors with extended π‐conjugation for further application as fluorescent materials.
Biological mechanism of post‐herpetic neuralgia: Evidence from multiple patho‐psychophysiological measures
Authors: Peng W.W. , Guo X.L. , Jin Q.Q. , Wei H. , Xia X.L. , Zhang Y. , Huang P.C. , Wang W.C. , Li S.L. , Wang J.S. , Chen J. , Hu L.
Published: December 2016

Background

Post‐herpetic neuralgia (PHN), which develops after the resolution of a herpes zoster eruption, is an exceptionally drug‐resistant neuropathic pain. The unsatisfactory management of PHN partly results from the difficulty in dissecting out its contributing factors due to the complexity of PHN mechanism.

Methods

Here, to elaborate our understanding of the PHN mechanism and to establish a basis for effective therapeutic strategies, we comprehensively investigated the contributions of multiple factors to PHN severity.

Results

Based on the comparison of somatosensory detection thresholds (C, Aδ and Aβ fibre thresholds) between affected and unaffected sides, 16 PHN patients with significant sensory deficits and 13 PHN patients without significant sensory deficits were identified and assigned to different groups. The different extents of lesions in the nociceptive system between patients with and without sensory deficits were confirmed using laser‐evoked brain responses. Moreover, patients with sensory deficits had more severe pain and psychological disorders, e.g. anxiety and depression. Importantly, chronic pain severity was significantly influenced by various psychophysiological factors (sleep disturbances, psychological disorders and hypothalamic‐pituitary‐adrenal axis dysfunction) for patients with sensory deficits.

Conclusions

Our findings demonstrated the contribution of multiple patho‐psychophysiological factors to PHN severity, which could help establish a basis for the development of a rational, patient‐centred therapeutic strategy.

Significance

This study revealed the contribution of multiple patho‐psychophysiological factors to PHN severity, which expanded our understanding of the underlying PHN mechanism, and helped develop a rational, patient‐centred therapeutic strategy targeting towards the corresponding etiology and psychophysiological disorders for individual patient.
Molecularly imprinted probe for solid‐phase extraction of hippuric and 4‐methylhippuric acids directly from human urine samples followed by MEKC analysis
Authors: Boscari Carolina Nasser , Mazzuia Giovanna Rodrigues , Wisniewski Célio , Borges Keyller Bastos , Figueiredo Eduardo Costa
Published: December 2016

Hippuric acid (HA) and 4‐methylhippuric acid (4‐MHA) are metabolites as well as biological indicators for toluene and xylenes, respectively, and their determination in urine samples is very important, in order to monitor the occupational exposition to these solvents, ensuring a safe working environment. Thus, this paper describes the synthesis and characterization of a probe impregnated with molecularly imprinted polymers (MIPs) for the solid‐phase extraction of HA and 4‐MHA directly from untreated urine samples followed by micellar electrokinetic chromatography (MEKC) analyses. The MIP probe selectivity was compared to the non‐imprinted polymer probe. The MEKC separations were carried out in 50 mmol/L sodium tetraborate pH 10.0/0.5 mmol/L cetyltrimethylammonium bromide aqueous solution, with a constant voltage of –15 kV. The system variables were optimized to provide ideal conditions for the extraction and desorption of the analytes, as well as for the MEKC analyses. The method was linear from 0.5 to 5.0 g/L for both analytes, with correlation coefficients > 0.994. Precisions and accuracies, expressed as relative standard deviation and relative error, were < 20.0 and within –15.4 to 16.6%, respectively, in accordance with the United States Food and Drug Administration recommendation. The MIP probe has proven to be simple, cheap, resistant, and synthetically reproducible, being successfully used to analyze both HA and 4‐MHA from real samples.
Solvent‐mediated nonelectrostatic ion–ion interactions predicting anomalies in electrophoresis
Authors: Goswami Prakash , Dhar Jayabrata , Ghosh Uddipta , Chakraborty Suman
Published: December 2016

We study the effects of solvent‐mediated nonelectrostatic ion–ion interactions on electrophoretic mobility of a charged spherical particle. To this end, we consider the case of low surface electrostatic potential resulting in the linearization of the governing equations, which enables us to deduce a closed‐form analytical solution to the electrophoretic mobility. We subsequently compare our results to the standard model using Henry's approach and report the changes brought about by the nonelectrostatic potential. The classical approach to determine the electrophoretic mobility underpredicts the particle velocity when compared with experiments. We show that this issue can be resolved by taking into account nonelectrostatic interactions. Our analysis further reveals the phenomenon of electrophoretic mobility reversal that has been experimentally observed in numerous previous studies.
Capillary transport of two immiscible fluids in presence of electroviscous retardation
Authors: Bandopadhyay Aditya , Mandal Shubhadeep , Chakraborty Suman
Published: December 2016

The transport of two immiscible electrolytes through a narrow confinement whose walls bear a finite surface potential is analyzed through a lumped model by considering the influence of a regulatory self‐induced axial electric field, termed as streaming potential. The presence of a surface charge on the channel walls culminates in the aqueous solutions carrying a net charge so as to make the overall system (channel and fluid) electrically neutral. The advection due to pressure driven flow or capillarity in the absence of any externally imposed electric field causes a preferential transport of net charged species. Thus, in order to render a net zero current through the system, there is an induced electric field which also retards the flow as a consequence of the force acting on the charged segments of fluid due to the streaming electric field. It is shown through a lumped model that for the situation of two distinct segments of fluids, the rate of front penetration into the capillary is strongly dependent on the relative conductivities of the two fluids. The streaming electric field evolves in accordance to the net conductivity of the channel and is responsible for dynamic changes in the retarding influence on the segments of fluid.
Modular fluidic resistors to enable widely tunable flow rate and fluidic switching period in a microfluidic oscillator
Authors: Dang Van Bac , Kim Sung‐Jin
Published: December 2016

Microfluidic systems with modular components are attractive alternatives to monolithically integrated microfluidic systems because of their flexibility. In this study, we apply the modular concept on a water‐head‐pressure‐driven microfluidic oscillator and obtain a widely tunable flow rate and fluidic switching period. Modular fluidic resistors can be easily mounted onto and demounted from a main chip by means of plastic male connectors. The connectors enable a leak‐free connection between the modular resistors and main chip (leakage pressure > 140 kPa). With modular resistors, we show independent control of the flow rate and flow switching period of the oscillator system in a wide range (2.5 s–6.4 h and 2 μL/min–2 mL/min). This modular approach can be used to enhance the flexibility of instruction‐embedded microfluidic circuits in which their operational range is limited.
Simple monitoring of cell leakiness and viability in Escherichia coli bioprocesses—A case study
Authors: Wurm David J. , Marschall Lukas , Sagmeister Patrick , Herwig Christoph , Spadiut Oliver
Published: December 2016

In a recently published study, we developed a simple methodology to monitor Escherichia coli cell integrity and lysis during bioreactor cultivations, where we intentionally triggered leakiness. In this follow‐up study, we used this methodology, comprising the measurement of extracellular alkaline phosphatase to monitor leakiness and flow cytometry to follow viability, to investigate the effect of process parameters on a recombinant E. coli strain producing the highly valuable vascular endothelial growth factor A165 (VEGF‐A165) in the periplasm. Since the amount of soluble product was very little (<500 μg/g dry cell weight), we directly linked the effect of the three process parameters temperature, specific uptake rate of the inducer arabinose and specific growth rate (μ) to cell integrity and viability. We found that a low temperature and a high μ were beneficial for cell integrity and that an elevated temperature resulted in reduced viability. We concluded that the recombinant E. coli cells producing VEGF‐A165 in the periplasm should be cultivated at low temperature and high μ to reduce leakiness and guarantee high viability. Summarizing, in this follow‐up study we demonstrate the usefulness of our simple methodology to monitor leakiness and viability of recombinant E. coli cells during bioreactor cultivations.
Variation in malathion sensitivity among populations of Blanchard's cricket frogs (Acris blanchardi) and implications for risk assessment
Authors: Hoskins Tyler D. , Boone Michelle D.
Published: December 2016

Intraspecific variability in contaminant sensitivity could undermine risk assessments for nontarget organisms such as amphibians. To test how amphibian populations vary in tolerance to anticipated lethal and sublethal exposures to a pesticide, we exposed Blanchard's cricket frogs (Acris blanchardi) from 3 populations across a broad portion of their range to the insecticide malathion. Exposure in mesocosms to a nominal concentration of 1 mg/L (measured concentrations at 1 h and 24 h postaddition of 0.160 mg/L and 0.062 mg/L, respectively), a realistic direct-overspray scenario, reduced survival to metamorphosis by 43% relative to controls and revealed variation in tolerance among populations. Survival ranged from 74% for the most tolerant population to 18% for the least tolerant population, a 4.1-fold difference. Mass at metamorphosis and time to metamorphosis were unaffected. Although malathion reduced zooplankton abundance, it did not alter food resources (periphyton or phytoplankton relative abundance), or a suite of water-quality variables (pH, temperature, and dissolved oxygen). A 96-h time-to-death assay designed to isolate direct, lethal effects also revealed variation in tolerance among populations. Time to death (mean ± standard error) ranged from 2.4 ± 0.18 h for the least tolerant population to 17.8 ± 4.72 h for the most tolerant population, a 7.4-fold difference. However, relative sensitivities of populations differed in the mesocosm and laboratory studies, which differed in exposure concentrations, suggesting that populations tolerant of high concentrations can be more sensitive to lower concentrations. We suggest that direct overspray could reduce larval survival in the field for this species. Studies assessing the role of contaminants in declines or extrapolating to untested populations, especially across large geographical regions, should quantify the range of intraspecific variation. Risk assessors could address intraspecific variability directly by using an intraspecific uncertainty factor. Environ Toxicol Chem 2017;36:1917–1923. © 2016 SETAC
Optimization of durum wheat bread enriched with bran
Authors: Saccotelli Maria A. , Conte Amalia , Burrafato Krystel R. , Calligaris Sonia , Manzocco Lara , Del Nobile Matteo A.
Published: December 2016

An attempt is made in this study to balance the nutritional and sensory quality of bread. In particular, the formulation of a functional durum wheat bread enriched with bran at high concentration has been developed. Organogel concentration and bran particle size have been used as process variables for bread optimization. Bran concentration was increased at value as high as 15%, thus increasing the nutritional content, even though the sensory quality decreased. Bread was scored barely acceptable at 15% bran concentration. Therefore, the organogel concentration and bran particle size have been optimized to enhance bread sensory quality. Results show that it is possible to prepare bread with a significant bran enrichment without compromising its acceptability by adding proper concentration of organogel and using bran in appropriate particles size.