bluuebunny/crossref_metadata_2025 huggingface dataset:
Dirhodium(II)‐Catalyzed Annulation of Enoldiazoacetamides with α‐Diazoketones: An Efficient and Highly Selective Approach to Fused and Bridged Ring Systems
Authors: Cheng Qing‐Qing , Yedoyan Julietta , Arman Hadi , Doyle Michael P.
Published: March 2016

A dirhodium(II)‐catalyzed annulation reaction between two structurally different diazocarbonyl compounds furnishes the donor–acceptor cyclopropane‐fused benzoxa[3.2.1]octane scaffold with excellent chemo‐, regio‐, and diastereoselectivity under exceptionally mild conditions. The composite transformation occurs by [3+2]‐cycloaddition between donor–acceptor cyclopropenes generated from enoldiazoacetamides and carbonyl ylides formed from intramolecular carbene–carbonyl cyclization in one pot with one catalyst. The annulation products can be readily transformed into benzoxa[3.3.1]nonane and hexahydronaphthofuran derivatives with exact stereocontrol. This method allows the efficient construction of three fused and bridged ring systems, all of which are important skeletons of numerous biologically active natural products.
Potassium 4,4′‐Bis(dinitromethyl)‐3,3′‐azofurazanate: A Highly Energetic 3D Metal–Organic Framework as a Promising Primary Explosive
Authors: Tang Yongxing , He Chunlin , Mitchell Lauren A. , Parrish Damon A. , Shreeve Jean'ne M.
Published: March 2016

Environmentally acceptable alternatives to toxic lead‐based primary explosives are becoming increasingly important for energetic materials. In this study, potassium 4,4′‐bis(dinitromethyl)‐3,3′‐azofurazanate, comprising two dinitromethyl groups and an azofurazan moiety, was synthesized and isolated as a new energetic 3D metal–organic framework (MOF). Several attractive properties, including a density of 2.039 g cm−3, a decomposition temperature of 229 °C, a detonation velocity of 8138 m s−1, a detonation pressure of 30.1 GPa, an impact sensitivity of 2 J, and friction sensitivity of 20 N make 4 a good candidate as a green primary explosive.
Membrane‐permeable Triphosphate Prodrugs of Nucleoside Analogues
Authors: Gollnest Tristan , Dinis de Oliveira Thiago , Rath Anna , Hauber Ilona , Schols Dominique , Balzarini Jan , Meier Chris
Published: March 2016

The metabolic conversion of nucleoside analogues into their triphosphates often proceeds insufficiently. Rate‐limitations can be at the mono‐, but also at the di‐ and triphosphorylation steps. We developed a nucleoside triphosphate (NTP) delivery system (TriPPPro‐approach). In this approach, NTPs are masked by two bioreversible units at the γ‐phosphate. Using a procedure involving H‐phosphonate chemistry, a series of derivatives bearing approved, as well as potentially antivirally active, nucleoside analogues was synthesized. The enzyme‐triggered delivery of NTPs was demonstrated by pig liver esterase, in human T‐lymphocyte cell extracts and by a polymerase chain reaction using a prodrug of thymidine triphosphate. The TriPPPro‐compounds of some HIV‐inactive nucleoside analogues showed marked anti‐HIV activity. For cellular uptake studies, a fluorescent TriPPPro‐compound was prepared that delivered the triphosphorylated metabolite to intact CEM cells.
Organophotocatalysis: Insights into the Mechanistic Aspects of Thiourea‐Mediated Intermolecular [2+2] Photocycloadditions
Authors: Vallavoju Nandini , Selvakumar Sermadurai , Pemberton Barry C. , Jockusch Steffen , Sibi Mukund P. , Sivaguru Jayaraman
Published: March 2016

Mechanistic investigations of the intermolecular [2+2] photocycloaddition of coumarin with tetramethylethylene mediated by thiourea catalysts reveal that the reaction is enabled by a combination of minimized aggregation, enhanced intersystem crossing, and altered excited‐state lifetime(s). These results clarify how the excited‐state reactivity can be manipulated through catalyst–substrate interactions and reveal a third mechanistic pathway for thiourea‐mediated organo‐photocatalysis.
Analyzing the Case for Bifunctional Catalysis
Authors: Andersen Mie , Medford Andrew J. , Nørskov Jens K. , Reuter Karsten
Published: March 2016

Bifunctional coupling of two different catalytic site types has often been invoked to explain experimentally observed enhanced catalytic activities. We scrutinize such claims with generic scaling‐relation‐based microkinetic models that allow exploration of the theoretical limits for such a bifunctional gain for several model reactions. For sites at transition‐metal surfaces, the universality of the scaling relations between adsorption energies largely prevents any improvements through bifunctionality. Only the consideration of systems that involve the combination of different materials, such as metal particles on oxide supports, offers hope for significant bifunctional gains.
Investigation of the physico‐mechanical properties of electrospun PVDF/cellulose (nano)fibers
Authors: Issa Ahmed A. , Al‐Maadeed Mariam , Luyt Adriaan S. , Mrlik Miroslav , Hassan Mohammad K.
Published: March 2016

The electro‐activity and mechanical properties of PVDF depends mainly on the β‐phase content and degree of crystallinity. In this study, cellulose fibers were used to improve these characteristics. This could be achieved because the hydroxyl groups on cellulose would force the fluorine atoms in PVDF to be in the trans‐conformation, and the cellulose particles could act as nucleation centers. Electrospinning was used to prepare the PVDF/cellulose (nano)fibrous films, and this improved the total crystallinity and the formation of β‐crystals. However, the presence and amount of cellulose in PVDF were found to have little influence on the β‐phase content and on the total crystallinity of PVDF. Improvements in the extent of crystallinity and the β‐phase content were primarily brought about by the chain‐ and crystal orientation as a result of electrospinning. The thermal stability of PVDF in the composites slightly increased with increasing cellulose content in the composites up to 1.0 wt %, while the modulus and tensile strength significantly increased up to the same filler level. The dielectric storage permittivity also increased with increasing cellulose content, but the presence of cellulose had no influence on the dynamics of the γ‐ and β‐relaxations of the PVDF. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2016,133, 43594.
Study of crystallization behavior of neat poly(vinylidene fluoride) and transcrystallization in carbon fiber/poly(vinylidene fluoride) composite under a temperature gradient
Authors: Zhang Shengnan , Wang Hai , Xu Duigong , Yang Wenxiao , Tang Ping , Bin Yuezhen
Published: March 2016

The crystallization behavior of poly(vinylidene fluoride) (PVDF) and transcrystallization in carbon fiber (CF)/PVDF composite were investigated under a temperature gradient. The crystallization temperature (Tc) was controlled in the range of 110–180 °C. For neat PVDF, the results showed that exclusive γ phase formed at Tc above 164 °C, but coexisted with α phase at Tc ranging from 137 to 160 °C. The promotion of γ phase to nucleation of α phase at low Tc was observed for the first time. For CF/PVDF composite, a cylindrical transcrystalline (TC) layer formed on the surface of CF when Tc was between 137 and 172 °C. The TC layer was exclusively composed of γ phase at Tc above 164 °C. The hybrid nucleation was dominated by γ phase though some α phase nuclei emerged on the surface of CF when Tc was in the range of 144–160 °C. As Tc decreased, competition between the hybrid nucleation of α and γ phase became more intense. The γ phase nuclei was soon circumscribed by the rapidly developed α phase when Tc was below 144 °C. Furthermore, some α phase nuclei were induced at the surface of the γ phase TC layer, and developed into α phase TC layer when Tc was in the range of 146–156 °C, which resulted in a doubled TC layer of α and γ phase at the interface of the composite. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43605.
Dynamic dependence networks: Financial time series forecasting and portfolio decisions
Authors: Zhao Zoey Yi , Xie Meng , West Mike
Published: March 2016

We discuss Bayesian forecasting of increasingly high‐dimensional time series, a key area of application of stochastic dynamic models in the financial industry and allied areas of business. Novel state‐space models characterizing sparse patterns of dependence among multiple time series extend existing multivariate volatility models to enable scaling to higher numbers of individual time series. The theory of thesedynamic dependence networkmodels shows how the individual series can bedecoupledfor sequential analysis and thenrecoupledfor applied forecasting and decision analysis. Decoupling allows fast, efficient analysis of each of the series in individual univariate models that are linked – for later recoupling – through a theoretical multivariate volatility structure defined by a sparse underlying graphical model. Computational advances are especially significant in connection with model uncertainty about the sparsity patterns among series that define this graphical model; Bayesian model averaging using discounting of historical information builds substantially on this computational advance. An extensive, detailed case study showcases the use of these models and the improvements in forecasting and financial portfolio investment decisions that are achievable. Using a long series of daily international currencies, stock indices and commodity prices, the case study includes evaluations of multi‐day forecasts and Bayesian portfolio analysis with a variety of practical utility functions, as well as comparisons against commodity trading advisor benchmarks. Copyright © 2016 John Wiley & Sons, Ltd.
Silk route to the acceptance and re‐implementation of bacteriophage therapy
Authors:   Expert round table on acceptance and re‐implementation of bacteriophage therapy
Published: March 2016

This multidisciplinary expert panel opinion on bacteriophage therapy has been written in the context of a society that is confronted with an ever‐increasing number of antibiotic resistant bacteria. To avoid the return to a pre‐antibiotic era, alternative treatments are urgently needed. The authors aim to contribute to the opinion formation of relevant stakeholders on how to potentially develop an infrastructure and legislation that paves the way for the acceptance and re‐implementation of bacteriophage therapy.
Balance between von Willebrand factor and ADAMTS13 following major partial hepatectomy
Authors: Groeneveld D J , Alkozai E M , Adelmeijer J , Porte R J , Lisman T
Published: March 2016

Background

Conventional coagulation tests are frequently prolonged after liver surgery, suggesting a postoperative bleeding tendency. At the same time, thrombotic complications following partial hepatectomy (PH) are not uncommon. Little is known about changes in the platelet adhesive protein von Willebrand factor (VWF) and its cleaving protease a disintegrin and metalloprotease with a thrombospondin type 1 motif, member 13 (ADAMTS13) following a PH.

Methods

Plasma samples were collected before and after PH and pylorus-preserving pancreaticoduodenectomy (PPPD), and from 24 healthy individuals. Plasma levels of VWF and ADAMTS13, VWF activity and VWF-dependent platelet adhesion were measured, and compared between the groups.

Results

Median (i.q.r.) VWF levels increased more after PH (17 patients) than following PPPD (10), reaching the highest level on postoperative day (POD) 3 (570 (473–656) versus 354 (305–476) per cent respectively; P = 0·009). VWF levels remained raised on POD 30. A decrease in median (i.q.r.) ADAMTS13 activity was observed for both patient groups, reaching the lowest level on POD 7 (24 (16–32) versus 38 (23–66) per cent for PH and PPPD respectively; P = 0·049), and levels remained significantly reduced at POD 30. VWF activity was significantly higher on day 7 following PH compared with PPPD (median (i.q.r.) 517 (440–742) versus 385 (322–484) per cent respectively; P = 0·009), and remained increased at POD 30. VWF-dependent platelet adhesion under conditions of flow was increased until POD 30 in patients after PH and PPPD, but was more pronounced in the PH group.

Conclusion

There are changes in the balance between VWF and ADAMTS13 levels and activity in patients after both PH and PPPD. Changes in the VWF–ADAMTS13 axis were more pronounced and of longer duration after PH than following PPPD.
Neutrophil to lymphocyte ratio as an indicator of the malignant behaviour of hepatocellular carcinoma
Authors: Okamura Y , Sugiura T , Ito T , Yamamoto Y , Ashida R , Mori K , Uesaka K
Published: March 2016

Background

The preoperative serum neutrophil to lymphocyte ratio (NLR) has been associated with survival in patients with hepatocellular carcinoma (HCC). However, it is still unclear what the NLR reflects precisely. This study aimed to elucidate the relationship between the NLR and TNM stage, and the role of NLR as a prognostic factor after liver resection for HCC.

Methods

This retrospective study enrolled patients who underwent liver resection as initial treatment for HCC. The best cut-off value of serum NLR was determined, and overall survival was compared among patients grouped according to TNM stage (I, II and III).

Results

The best cut-off value for NLR was 2·8. A high preoperative NLR was more frequently associated with poor overall survival than a low preoperative NLR after resection for TNM stage I tumours (5-year survival 45·0 versus 76·4 per cent, P < 0·001), but not stage II (P = 0·283) or stage III (P = 0·155) tumours. Among patients with TNM stage I disease, the proportion of patients with extrahepatic recurrence was greater in the group with a high preoperative NLR than in the low-NLR group (P = 0·006). In multivariable analysis, preoperative NLR was the strongest independent prognostic risk factor for overall survival in TNM stage I (hazard ratio 2·69, 95 per cent c.i. 1·57 to 4·59; P < 0·001).

Conclusion

Preoperative NLR was an important prognostic factor for TNM stage I HCC after liver resection with curative intent. These results suggest that the NLR may reflect the malignant potential of HCC.
Role of bone scan in addition to CT in patients with breast cancer selected for systemic staging
Authors: McCartan D P , Prichard R S , MacDermott R J , Rothwell J , Geraghty J , Evoy D , Quinn C M , Skehan S J , O'Doherty A , McDermott E W
Published: March 2016

Background

The majority of women with breast cancer present with localized disease. The optimal strategy for identifying patients with metastatic disease at diagnosis remains unclear. The aim of this study was to evaluate the additional diagnostic yield from isotope bone scanning when added to CT staging of the thorax, abdomen and pelvis (CT-TAP) in patients with newly diagnosed breast cancer.

Methods

All patients diagnosed with breast cancer who underwent staging CT-TAP and bone scan between 2011 and 2013 were identified from a prospective database of a tertiary referral breast cancer centre that provides a symptomatic and population-based screening breast service. Criteria for staging included: biopsy-proven axillary nodal metastases; planned neoadjuvant chemotherapy or mastectomy; locally advanced or inflammatory breast cancer and symptoms suggestive of metastases.

Results

A total of 631 patients underwent staging by CT-TAP and bone scan. Of these, 69 patients (10·9 per cent) had distant metastasis at presentation, with disease confined to a single organ in 49 patients (71 per cent) and 20 (29 per cent) having metastatic deposits in multiple organs. Bone metastasis was the most common site; 39 of 49 patients had bone metastasis alone and 12 had a single isolated metastatic deposit. All but two of these were to the axial skeleton. No preoperative histological factors identified a cohort of patients at risk of metastatic disease. Omission of the bone scan in systemic staging would have resulted in a false-negative rate of 0·8 per cent.

Conclusion

For patients diagnosed with breast cancer, CT-TAP is a satisfactory stand-alone investigation for systemic staging.
Systematic review and meta-analysis of the diagnostic accuracy of ductoscopy in patients with pathological nipple discharge
Authors: Waaijer L , Simons J M , Borel Rinkes I H M , van Diest P J , Verkooijen H M , Witkamp A J
Published: March 2016

Background

Invasive surgery remains the standard for diagnosis of pathological nipple discharge (PND). Only a minority of patients with nipple discharge and an unsuspicious finding on conventional breast imaging have cancer. Ductoscopy is a minimally invasive alternative for evaluation of PND. This systematic review and meta-analysis was designed to evaluate the diagnostic accuracy of ductoscopy in patients with PND.

Methods

A systematic search of electronic databases for studies addressing ductoscopy in patients with PND was conducted. Two classification systems were assessed. For DSany, all visualized ductoscopic abnormalities were classified as positive, whereas for DSsusp, only suspicious findings were considered positive. After checking heterogeneity, pooled sensitivity and specificity of DSany and DSsusp were calculated.

Results

The search yielded 4642 original citations, of which 20 studies were included in the review. Malignancy rates varied from 0 to 27 per cent. Twelve studies, including 1994 patients, were eligible for meta-analysis. Pooled sensitivity and specificity of DSany were 94 (95 per cent c.i. 88 to 97) per cent and 47 (44 to 49) per cent respectively. Pooled sensitivity and specificity of DSsusp were 50 (36 to 64) and 83 (81 to 86) per cent respectively. Heterogeneity between studies was moderate to large for sensitivity (DSany: I2 = 17·5 per cent; DSsusp: I2 = 37·9 per cent) and very large for specificity (DSany: I2 = 96·8 per cent; DSsusp: I2 = 92·6 per cent).

Conclusion

Ductoscopy detects about 94 per cent of all underlying malignancies in patients with PND, but does not permit reliable discrimination between malignant and benign findings.
Deficits in Visual System Functional Connectivity after Blast‐Related Mild TBI are Associated with Injury Severity and Executive Dysfunction
Authors: Gilmore Casey S. , Camchong Jazmin , Davenport Nicholas D. , Nelson Nathaniel W. , Kardon Randy H. , Lim Kelvin O. , Sponheim Scott R.
Published: March 2016

Introduction

Approximately, 275,000 American service members deployed to Iraq or Afghanistan have sustained a mild traumatic brain injury (mTBI), with 75% of these incidents involving an explosive blast. Visual processing problems and cognitive dysfunction are common complaints following blast‐related mTBI.

Methods

In 127 veterans, we examined resting fMRI functional connectivity (FC) of four key nodes within the visual system: lateral geniculate nucleus (LGN), primary visual cortex (V1), lateral occipital gyrus (LO), and fusiform gyrus (FG). Regression analyses were performed (i) to obtain correlations between time‐series from each seed and all voxels in the brain, and (ii) to identify brain regions in which FC variability was related to blast mTBI severity. Blast‐related mTBI severity was quantified as the sum of the severity scores assigned to each of the three most significant blast‐related injuries self‐reported by subjects. Correlations between FC and performance on executive functioning tasks were performed across participants with available behavioral data (n = 94).

Results

Greater blast mTBI severity scores were associated with lower FC between: (A) LGN seed and (i) medial frontal gyrus, (ii) lingual gyrus, and (iii) right ventral anterior nucleus of thalamus; (B) V1 seed and precuneus; (C) LO seed and middle and superior frontal gyri; (D) FG seed and (i) superior and medial frontal gyrus, and (ii) left middle frontal gyrus. Finally, lower FC between visual network regions and frontal cortical regions predicted worse performance on the WAIS digit‐symbol coding task.

Conclusion

These are the first published results that directly illustrate the relationship between blast‐related mTBI severity, visual pathway neural networks, and executive dysfunction – results that highlight the detrimental relationship between blast‐related brain injury and the integration of visual sensory input and executive processes.
Neuroanatomical variation in autism spectrum disorder: A comprehensive review
Authors: Jumah Fareed , Ghannam Malik , Jaber Mohammad , Adeeb Nimer , Tubbs R. Shane
Published: March 2016

Autism Spectrum Disorder (ASD) is a neurodevelopmental disorder characterized by impairments in socialization, communication, and behavior. Many investigators have described the anatomical abnormalities in autistic brains, in an attempt to correlate them with the manifestations of ASD. Herein, we reviewed all the available literature about the neuroanatomical findings in ASD available via “PubMed” and “Google Scholar.” References found in review articles were also searched manually. There was substantial discrepancy throughout the literature regarding the reported presence and significance of neuroanatomical findings in ASD, and this is thoroughly discussed in the present review. Clin. Anat. 29:454–465, 2016. © 2016 Wiley Periodicals, Inc.
Outcome of patients with nonmetastatic muscle‐invasive bladder cancer not undergoing cystectomy after treatment with noncisplatin‐based chemotherapy and/or radiotherapy: a retrospective analysis
Authors: Bamias Aristotle , Tsantoulis Petros , Zilli Thomas , Papatsoris Athanasios , Caparrotti Francesca , Kyratsas Christos , Tzannis Kimon , Stravodimos Kostas , Chrisofos Michael , Wirth Gregory J. , Skolarikos Andreas , Mitropoulos Dionysios , Constantinides Constantinos A. , Deliveliotis Charalambos , Iselin Christophe E. , Miralbell Raymond , Dietrich Pierre‐Yves , Dimopoulos Meletios A.
Published: March 2016

Transurethral resection of bladder tumor (TURBT), radiotherapy, chemotherapy, or combinations can be used in patients with muscle‐invasive bladder cancer (MIBC) not undergoing cystectomy. Nevertheless, unfitness for cystectomy is frequently associated with unfitness for other therapeutic modalities. We report the outcome of patients with MIBC who did not undergo cystectomy and did not receive cisplatin‐based chemotherapy. Selection criteria for the study were nonmetastatic MIBC, no cystectomy, no cisplatin‐based chemotherapy. Chemotherapy and/or radiotherapy should have been used aside from TURBT. Forty‐nine patients (median age 79), managed between April 2001 and January 2012, were included in this analysis. Median Charlson Comorbidity Index was 5, while 76% were unfit for cisplatin. Treatment included radiotherapy (n = 7), carboplatin‐based chemotherapy (n = 25), carboplatin‐based chemotherapy followed by radiotherapy (n = 10), and radiochemotherapy (n = 7). Five‐year event‐free rate was 26% (standard error [SE] = 7) for overall survival, 23% (SE = 7) for progression‐free survival, and 30 (SE = 8) for cancer‐specific survival (CSS). Patients who were treated with combination of radiotherapy and chemotherapy had significantly longer CSS compared to those treated with radiotherapy or chemotherapy only (5‐year CSS rate: 16% [SE 8] vs. 63% [SE 15], P = 0.053). Unfit‐for‐cystectomy patients frequently receive suboptimal nonsurgical treatment. Their outcome was poor. Combining chemotherapy with radiotherapy produced better outcomes and should be prospectively evaluated.
The actin‐binding ERM protein Moesin directly regulates spindle assembly and function during mitosis
Authors: Vilmos Péter , Kristó Ildikó , Szikora Szilárd , Jankovics Ferenc , Lukácsovich Tamás , Kari Beáta , Erdélyi Miklós
Published: March 2016

Ezrin‐Radixin‐Moesin proteins are highly conserved, actin‐binding cytoskeletal proteins that play an essential role in microvilli formation, T‐cell activation, and tumor metastasis by linking actin filaments to the plasma membrane. Recent studies demonstrated that the only Ezrin‐Radixin‐Moesin protein of Drosophila melanogaster, Moesin, is involved in mitotic spindle function through stabilizing cell shape and microtubules at the cell cortex. We previously observed that Moesin localizes to the mitotic spindle; hence, we tested for the biological significance of this surprising localization and investigated whether it plays a direct role in spindle function. To separate the cortical and spindle functions of Moesin during mitosis we combined cell biological and genetic methods. We used early Drosophila embryos, in which mitosis occurs in the absence of a cell cortex, and found in vivo evidence for the direct requirement of Moesin in mitotic spindle assembly and function. We also found that the accumulation of Moesin precedes the construction of the microtubule spindle, and the fusiform structure formed by Moesin persists even after the microtubules have disassembled.
High‐Valent‐Cobalt‐Catalyzed C−H Functionalization Based on Concerted Metalation–Deprotonation and Single‐Electron‐Transfer Mechanisms
Authors: Wei Donghui , Zhu Xinju , Niu Jun‐Long , Song Mao‐Ping
Published: March 2016

C−H functionalization has been established as a powerful strategy for the commercial construction of organic molecules. This review encompasses the most recent advances in C−H activation catalyzed by earth‐abundant cobalt complexes, involving two types of fundamental reaction paths, that is, the concerted metalation–deprotonation (CMD) path associated with non‐oxidative C−H activation and the intermolecular single‐electron‐transfer (SET) path. Transformations catalyzed by high‐valent cobalt based on the two mechanisms and used in organic syntheses, including those involving C−C and C−X (X=O and N) bond formation, are herein presented.
Pillared Sn‐MWW Prepared by a Solid‐State‐Exchange Method and its Use as a Lewis Acid Catalyst
Authors: Ren Limin , Guo Qiang , Orazov Marat , Xu Dandan , Politi Dorothea , Kumar Prashant , Alhassan Saeed M. , Mkhoyan K. Andre , Sidiras Dimitrios , Davis Mark E. , Tsapatsis Michael
Published: March 2016

Pillared Sn‐MWW (Sn‐MWW(SP)‐SSE) was prepared through a solid‐state‐exchange (SSE) route. The pillared structure was inherited from pillared B‐MWW, and Sn was inserted in the framework by boron leaching and solid‐state‐exchange with tin tetrachloride pentahydrate. The Sn‐MWW(SP)‐SSE with framework Sn sites exhibits Lewis acidity and good catalytic performance for the Baeyer–Villiger oxidation, and mono‐ and disaccharide isomerizations.
Helical Nano‐crystallite (HNC) Phases: Chirality Synchronization of Achiral Bent‐Core Mesogens in a New Type of Dark Conglomerates
Authors: Alaasar Mohamed , Prehm Marko , Tschierske Carsten
Published: March 2016

Spontaneous generation of macroscopic homochirality in soft matter systems by self‐assembly of exclusively achiral molecules under achiral conditions is a challenging task with relevance for fundamental scientific research and technological applications. Dark conglomerate phases (DC phases), being optically isotropic mesophases composed of conglomerates of macroscopic chiral domains and formed by some non‐chiral bent‐core mesogens, represent such a case. Here we report two new series of non‐symmetric bent‐core molecules capable of forming a new type of mirror symmetry broken DC phases. In the synthesized molecules, a bent 4‐bromoresorcinol core is connected to a phenyl benzoate wing and an azobenzene wing with or without additional peripheral fluorine substitution. The self‐assembly was investigated by DSC, polarizing microscopy, electro‐optical studies and XRD. Chiral and apparently achiral DC phases were observed besides distinct types of lamellar liquid crystalline phases with different degree of polar order, allowing the investigation of the transition from smectic to DC phases. This indicates a process in which increased packing density at first gives rise to restricted rotation and thus to growing polar order, which then leads to chirality synchronization, layer frustration and nano‐scale crystallization. Topological constraints arising from the twisted packing of helical conformers in lamellar crystals is proposed to lead to amorphous solids composed of helical nano‐crystallites with short coherence length (HNC phases). This is considered as a third major type of DC phases, distinct from the previously known liquid crystalline sponge phases and the helical nano‐filament phases (HNF phases). Guidelines for the molecular design of new materials capable of self‐assembly into these three types of DC phases are proposed.
Bimetallic Gold(I) Complexes with Ethynyl‐Helicene and Bis‐Phosphole Ligands: Understanding the Role of Aurophilic Interactions in their Chiroptical Properties
Authors: El Sayed Moussa Mehdi , Chen Hui , Wang Zuoyong , Srebro‐Hooper Monika , Vanthuyne Nicolas , Chevance Soizic , Roussel Christian , Williams J. A. Gareth , Autschbach Jochen , Réau Régis , Duan Zheng , Lescop Christophe , Crassous Jeanne
Published: March 2016

Monometallic gold(I)‐alkynyl‐helicene complexes (1 a,b) and bimetallic gold(I)‐alkynyl‐helicene architectures featuring the presence (2 a,b) or absence (3 a,b) of aurophilic intramolecular interactions were prepared by using different types of phosphole ligands (mono‐phosphole L1 or bis‐phospholes L2,3). The influence of the AuI d10 metal center(s) on the electronic, photophysical, and chiroptical properties of these unprecedented phosphole‐gold(I)‐alkynyl‐helicene complexes was examined. Experimental and theoretical results highlight the importance of ligand‐to‐ligand‐type charge transfers and the strong effect of the presence or absence of AuI–AuI interactions in 2 a,b.
Several Enantiopure Chiral Building Blocks Derived from D‐Mannose and a Formal Synthesis of Dubiusamine C
Authors: Tan Dongxing , Xu Murong , Xu Zejun , Wu Yikang , You Jun
Published: March 2016

Several multi‐functional chiral building blocks derived from D‐mannose are developed, which may find diverse utilities as sources of 1‐hydroxy‐3‐methyl structural units in enantioselective synthesis of many natural products. A formal synthesis of natural dubiusamine‐C is also presented.
Hit Identification of a Novel Dual Binder for h‐telo/c‐myc G‐Quadruplex by a Combination of Pharmacophore Structure‐Based Virtual Screening and Docking Refinement
Authors: Rocca Roberta , Costa Giosuè , Artese Anna , Parrotta Lucia , Ortuso Francesco , Maccioni Elias , Pinato Odra , Greco Maria Laura , Sissi Claudia , Alcaro Stefano , Distinto Simona , Moraca Federica
Published: March 2016

It is well known that G‐quadruplexes are targets of great interest for their roles in crucial biological processes, such as aging and cancer. Hence, a promising strategy for anticancer drug therapy is the stabilization of these structures by small molecules. We report a high‐throughput in silico screening of commercial libraries from several different vendors by means of a combined structure‐based pharmacophore model approach followed by docking simulations. The compounds selected by the virtual screening procedure were then tested for their ability to interact with human telomeric G‐quadruplex folding by circular dichroism, fluorescence spectroscopy, and fluorescence intercalator displacement. Our approach resulted in the identification of a 13‐[(dimethylamino)methyl]‐12‐hydroxy‐8H‐benzo[c]indolo[3,2,1‐ij][1,5]naphthyridin‐8‐one derivative as a novel promising stabilizer of G‐quadruplex structures within the human telomeric and the c‐myc promoter sequences.
Systematic approach for deriving feasible mappings of parallel algorithms to parallel computing platforms
Authors: Arkin Ethem , Tekinerdogan Bedir , İmre Kayhan M.
Published: March 2016

The need for high‐performance computing together with the increasing trend from single processor to parallel computer architectures has leveraged the adoption of parallel computing. To benefit from parallel computing power, usually parallel algorithms are defined that can be mapped and executed on parallel computing platforms. In general, different alternative mappings can be defined each with different performance. For small computing platforms with a limited number of processing nodes, the mapping process can be carried out manually. However, for large‐scale parallel computing platforms in which hundreds of thousands of processing nodes are applied, the number of possible mapping alternatives increases dramatically, and the mapping process becomes intractable for the human engineer. To assist the parallel computing engineer, we provide a systematic approach to derive feasible mapping alternatives of parallel algorithms to parallel computing platforms. The approach includes activities for modeling the parallel algorithm and parallel computing platform, generation of feasible mapping alternatives, generation of the deployment code, and finally the deployment of the generated code to the nodes. We evaluate our approach for deriving feasible mapping alternatives for four well‐known parallel algorithms. The evaluation is based on both simulations and real executions of the generated mapping alternatives. Copyright © 2016 John Wiley & Sons, Ltd.
Survival rate of teeth with periodontally hopeless prognosis after therapies with intentional replantation and perioprosthetic procedures ‐ a study of case series for 5–12 years
Authors: Hou Guey‐Lin , Hou Lein‐Tuan , Weisgold Arnold
Published: March 2016

The purpose of the present study was to evaluate the longitudinal survival rate of the treatment of teeth affected with periodontally hopeless prognosis and secondary occlusal traumatism (SOT) using intentional replantation (IR) and periodontal prosthesis. We collected data from 17 individuals who received IR and participated in the study during 1995 to 2014. Of the 17 teeth affected by periodontally extreme conditions with deep angular bone defects, severe alveolar bone loss extending to or beyond the apex, and SOT, was recognized as having hopeless prognosis. Those teeth were treated sequentially using procedures that included basic periodontal therapy, therapeutic provisional prosthesis, IR, fixed dental prosthesis, crown and sleeve‐coping telescopic dentures (CSCTDs), or fixed prosthesis and CSCTD combined. Longitudinal assessments of clinical parameters and radiographic bone change before and after IR were evaluated. Clinical results showed that the overall cumulative survival rate of assayed teeth after IR therapy (5–12 years) was 88.2%. The mean (±SD) estimated radiographic alveolar bone loss was 12.7 ± 2.1 mm (88.5% ± 13.3%) of the root length, initially, and estimated radiographic alveolar bone gain was 4.0 ± 2.2 mm ultimately, in 17 replanted teeth with SOT. Only one tooth (5.9%) exhibited root resorption. Ankylosis was not observed during the study. Periapical radiographs demonstrated that satisfactory periodontal healing of lamina dura and bone fills occurred in all replanted teeth with SOT. Generally, tooth mobility and SOT were significantly improved after therapy. Most treated teeth functioned well and remained stable clinically throughout the periods of study. The present study documented a promising outcome for autogenous IR and periprosthetic therapy of 17 periodontally hopeless teeth for 5–12 years. The present study revealed good bone gain and elimination of SOT and prominent occlusal function. We concluded that the application of IR, minocycline‐HCL and periodontal prosthetic procedures later elevated the prognosis of these otherwise hopeless teeth with SOT, which are valuable options for retaining teeth with periodontally extreme situations.
Prevalence of furcation‐involved molars in a Swedish adult population. A radiographic epidemiological study
Authors: Najim Uday , Slotte Christer , Norderyd Ola
Published: March 2016

The purpose of this study was to identify the prevalence of molars with furcation involvements grades II and III in adults participating in the Jönköping Oral Health Study 2003. The second aim was to study correlations between different variables and the presence of furcation involvement in these individuals. The present study was performed using bitewing and apical radiographs from 329 subjects. Furcations were considered healthy if the furcation was filled with bone up to the fornix. Two thousand fourteen molars fulfilled the inclusion criteria. The prevalence of molars with furcation involvements was 8.3%. Univariate analysis showed that plaque, age, and presence of periodontal pockets were significantly correlated with furcation‐involved molar/s (P ˂ 0.0001). Gingivitis and education were also significantly correlated to the presence of furcation involvement (P ˂ 0.006) and (P ≤ 0.01), respectively. Gender had no association with presence of involvements. Multivariate analysis showed that age and presence of periodontal pockets were significantly correlated with furcation involvement (P ˂ 0.0001). Smoking was also found to be associated with furcation involvement (P ˂ 0.04). The tooth most frequently and least likely displaying furcation involvement was the maxillary first molar and the mandibular second molar, respectively. Periodontal pockets, age, and smoking were risk indicators for furcation involvement.
A single‐stage LED streetlight driver with PFC and digital PWM dimming capability
Authors: Cheng Chun‐An , Chung Tsung‐Yuan
Published: March 2016

This paper proposes a single‐stage light‐emitting diode (LED) driver that offers power‐factor correction and digital pulse–width modulation (PWM) dimming capability for streetlight applications. The presented LED streetlight driver integrates an alternating current–direct current (AC–DC) converter with coupled inductors and a half‐bridge‐type LLC DC–DC resonant converter into a single‐stage circuit topology. The sub‐circuit of the AC–DC converter with coupled inductors is designed to be operated in discontinuous‐conduction mode for achieving input‐current shaping. Zero‐voltage switching of two active power switches and zero‐current switching of two output‐rectifier diodes in the presented LED driver decrease the switching losses; thus, the circuit efficiency is increased. A prototype driver for powering a 144‐W‐rated LED streetlight module with input utility‐line voltages ranging from 100 to 120 V is implemented and tested. The proposed streetlight driver features cost‐effectiveness, high circuit efficiency, high power factor, low levels of input‐current harmonics, and a digital PWM dimming capability ranging from 20% to 100% output rated LED power, which is fulfilled by a micro‐controller. Satisfying experimental results, including dimming tests, verify the feasibility of the proposed LED streetlight driver. Copyright © 2016 John Wiley & Sons, Ltd.
Get your campus ready for Generation Z
Authors: Hope Joan
Published: March 2016

WASHINGTON, D.C. — If you've noticed a shift in your traditional‐aged students' behaviors and expectations in the last couple of years, that's because you're seeing Generation Z arrive on campus. The first students from this generation started as freshmen in 2013, said Corey Seemiller, assistant professor of leadership studies at Wright State University; and Meghan Grace, new member orientation director for Sigma Phi Epsilon. Seemiller and Grace, the authors of Generation Z Goes to College, spoke at the Association of American Colleges and Universities annual meeting.
Age‐related changes in the effects of stress in pregnancy on infant motor development by maternal report: The Queensland Flood Study
Authors: Simcock Gabrielle , Kildea Sue , Elgbeili Guillaume , Laplante David P. , Stapleton Helen , Cobham Vanessa , King Suzanne
Published: March 2016

The current study examined the effects of a natural disaster (a sudden onset flood) as a stressor in pregnancy on infant fine and gross motor development at 2, 6, and 16 months of age. Whether the timing of the stressor in pregnancy or sex of the infant moderated the impact of the prenatal maternal stress on motor development was also explored. Mothers' objective experiences of the flood, emotional reactions and distress, and their cognitive appraisal of the event were assessed retrospectively. Infants' fine and gross motor skills were assessed with the Ages and Stages Questionnaire, and results showed age‐related changes in the effects of prenatal maternal stress on these domains. At 2 months, higher levels of prenatal maternal stress was positively related to infant motor development, yet at 6 and 16 months of age there was a negative association, particularly if flood exposure occurred later in pregnancy and if mothers had negative cognitive appraisals of the event. Results also showed differential effects of the maternal stress responses to the floods on infants' fine and gross motor development at each age and that infant sex did not buffer these effects. © 2016 Wiley Periodicals, Inc. Dev Psychobiol 58: 640–659, 2016.
Behaviour of hygrine and cuscohygrine in illicit cocaine production establishes their use as markers for chewing coca leaves in contrast with cocaine abuse
Authors: Rubio Nelida Cristina , Thurmann Denise , Krumbiegel Franziska , Pragst Fritz
Published: March 2016

Hygrine (HYG) and cuscohygrine (CUS) are natural alkaloids of coca leaves but are not found in illicit cocaine seizures. Therefore, they were proposed as markers for coca chewing in contrast to cocaine abuse in urine and hair testing. In order to examine at which step of the illegal cocaine production these compounds are lost, coca leaves were processed according to an authentic procedure by extraction with lime and kerosene, re‐extraction with sulphuric acid, and precipitation of coca paste with ammonia. Non‐extracted and extracted coca leaves, acidic extract and coca paste were analyzed by gas chromatography‐mass spectrometry (GC‐MS) and liquid chromatography‐tandem mass spectrometry (LC‐MS/MS) for cocaine, ecgonine methyl ester (EME), cinnamoylcocaine (CIN), HYG, and CUS. It follows from the results that under these conditions, HYG and CUS are extracted only to a minor extent by kerosene and are not precipitated from the acidic re‐extract in the coca paste. Due to this behaviour in illegal cocaine production, they fulfil the conditions as markers for coca chewing in an optimal way. However, for unambiguous discrimination between coca chewing and cocaine abuse in human samples, additional markers of manufactured cocaine are required. Copyright © 2016 John Wiley & Sons, Ltd.
Morphological and niche divergence of pinyon pines
Authors: Ortiz‐Medrano Alejandra , Scantlebury Daniel Patrick , Vázquez‐Lobo Alejandra , Mastretta‐Yanes Alicia , Piñero Daniel
Published: March 2016

The environmental variables that define a species ecological niche should be associated with the evolutionary patterns present in the adaptations that resulted from living in these conditions. Thus, when comparing across species, we can expect to find an association between phylogenetically independent phenotypic characters and ecological niche evolution. Few studies have evaluated how organismal phenotypes might mirror patterns of niche evolution if these phenotypes reflect adaptations. Doing so could contribute on the understanding of the origin and maintenance of phenotypic diversity observed in nature. Here, we show the pattern of niche evolution of the pinyon pine lineage (Pinus subsection Cembroides); then, we suggest morphological adaptations possibly related to niche divergence, and finally, we test for correlation between ecological niche and morphology. We demonstrate that niche divergence is the general pattern within the clade and that it is positively correlated with adaptation.
CD5 expression is regulated during human T‐cell activation by alternative polyadenylation, PTBP1, and miR‐204
Authors: Domingues Rita G. , Lago‐Baldaia Inês , Pereira‐Castro Isabel , Fachini Joseph M. , Oliveira Liliana , Drpic Danica , Lopes Nair , Henriques Telmo , Neilson Joel R. , Carmo Alexandre M. , Moreira Alexandra
Published: March 2016

T lymphocytes stimulated through their antigen receptor (TCR) preferentially express mRNA isoforms with shorter 3´ untranslated regions (3´‐UTRs) derived from alternative pre‐mRNA cleavage and polyadenylation (APA). However, the physiological relevance of APA programs remains poorly understood. CD5 is a T‐cell surface glycoprotein that negatively regulates TCR signaling from the onset of T‐cell activation. CD5 plays a pivotal role in mediating outcomes of cell survival or apoptosis, and may prevent both autoimmunity and cancer. In human primary T lymphocytes and Jurkat cells we found three distinct mRNA isoforms encoding CD5, each derived from distinct poly(A) signals (PASs). Upon T‐cell activation, there is an overall increase in CD5 mRNAs with a specific increase in the relative expression of the shorter isoforms. 3´‐UTRs derived from these shorter isoforms confer higher reporter expression in activated T cells relative to the longer isoform. We further show that polypyrimidine tract binding protein (PTB/PTBP1) directly binds to the proximal PAS and PTB siRNA depletion causes a decrease in mRNA derived from this PAS, suggesting an effect on stability or poly(A) site selection to circumvent targeting of the longer CD5 mRNA isoform by miR‐204. These mechanisms fine‐tune CD5 expression levels and thus ultimately T‐cell responses.
Antigen‐specific TIL therapy for melanoma: A flexible platform for personalized cancer immunotherapy
Authors: Kelderman Sander , Heemskerk Bianca , Fanchi Lorenzo , Philips Daisy , Toebes Mireille , Kvistborg Pia , van Buuren Marit M. , van Rooij Nienke , Michels Samira , Germeroth Lothar , Haanen John B. A. G. , Schumacher N. M.
Published: March 2016

Tumor infiltrating lymphocyte (TIL) therapy has shown objective clinical response rates of 50% in stage IV melanoma patients in a number of clinical trials. Nevertheless, the majority of patients progress either directly upon therapy or after an initial period of tumor control. Recent data have shown that most TIL products that are used for therapy contain only low frequencies of T cells reactive against known melanoma‐associated epitopes. Because of this, the development of a technology to create T‐cell products that are enriched for reactivity against defined melanoma‐associated antigens would seem valuable, both to evaluate the tumoricidal potential of T cells directed against different antigen classes and to potentially increase response rates. Here, we developed and validated a conditional MHC streptamer‐based platform for the creation of TIL products with defined antigen reactivities. We have used this platform to successfully enrich both high‐frequency (≥1%) and low‐frequency (<1%) tumor‐specific CD8+ T‐cell populations, and thereby created T‐cell products with enhanced tumor recognition potential. Collectively, these data demonstrate that selection of antigen‐specific T‐cell populations can be used to create defined T‐cell products for clinical use. This strategy thus forms a highly flexible platform for the development of antigen‐specific cell products for personalized cancer immunotherapy.