bluuebunny/crossref_metadata_2025 huggingface dataset:
Analysis Of The KLIC-score; An Outcome Predictor Tool For Prosthetic Joint Infections Treated With Debridement, Antibiotics And Implant Retention
Authors: Duffy Sean DX , Ahearn Nathanael , Darley Elizabeth SR , Porteous Andrew J , Murray James R , Howells Nicholas R
Published: August 2018

Abstract. Background: Debridement, antibiotics and implant retention (DAIR) forms the primary treatment modality for early prosthetic joint infection (PJI). The KLIC score has been proposed as a risk stratification tool for use in predicting outcome of prosthetic knee infections. Our aim was to determine the accuracy of this scoring system at an independent tertiary PJI centre in a typical DAIR population.Methods: Between 2008 and 2015, patients with infected knee prostheses treated with DAIR were identified. The patient notes and blood tests were reviewed retrospectively and the 'KLIC-score' was calculated and correlated with outcome. The end point for early failure was defined as: 1) the need for unscheduled surgery, 2) infection-related death ≤12 months from debridement or 3) the need for suppressive antibiotic treatment.Results: 59 patients received DAIR procedures for knee PJI. Treatment was successful in 41 patients (69%) with early failure in 18 patients (31%). Patients deemed high-risk (KLIC-score ≥7) had notably higher failure rates (60%) than those scoring <7 (28%). No relationship can be drawn between KLIC-scores of <7 and failure rates.Conclusions: The KLIC-score applied retrospectively was able to predict patients with the highest risk of early failure but provides little information in patients with scores of <7.
Qualitative Alpha-defensin Versus The Main Available Tests For The Diagnosis Of Periprosthetic Joint Infection: Best Predictor Test?
Authors: Riccio Giovanni , Cavagnaro Luca , Akkouche Wassim , Carrega Giuliana , Felli Lamberto , Burastero Giorgio
Published: August 2018

Abstract. Introduction: Biomarkers such as α-defensin demonstrated to be a potentially useful option in periprosthetic joint infection (PJI) diagnosis. Recently, a new point-of-care test for α-defensin level detection in synovial fluid has been commercialized in Europe. The aim of this study is to compare the α-defensin test (SynovasureTM) diagnostic ability with the main available clinical tests for periprosthetic joint infection diagnosis in a practical clinical setting of a Bone Infection Unit.Methods: Between 2015 and 2017, 146 patients with suspected chronic PJI were screened with SynovasureTM. Seventy-three of these met the Musculoskeletal Infection Society (MSIS) criteria and were included in the analysis. According to MSIS criteria, 40 patients (54.7%) were classified as infected and 33 (45.3%) as not infected. The results obtained with SynovasureTM were recorded and compared with standard diagnostic methods for PJI diagnosis.Results: SynovasureTM showed a sensitivity of 85.0 % (95% CI 70.2 to 94.3) and a specificity of 96.9 % (95% CI 83.8 to 99.9) for PJI detection. The positive likelihood ratio of SynovasureTM was 27.2 (95% CI 3.9 to 188.1) and the negative likelihood ratio was 0.2 (95% CI 0.1 to 0.3). The diagnostic odds ratio was 181.3 (95% CI 20.7 to 1590.4). SynovasureTM demonstrated a statistical significant difference when compared to Erythrocyte Sedimentation Rate (ESR) and C-reactive Protein (CRP) specificity (at least one positive test) and preoperative culture sensitivity (1 positive culture).Conclusion: Our findings show that SynovasureTM sensitivity is lower than quantitative α-D test, but when compared to the main available tests shows a good specificity and the highest DOR. On the SF it is the easier test to do, due to the fact that it needs a minimal amount of SF and it is not limited by blood contamination or antibiotic use. Whereas there is no single standalone test, SynovasureTM should be considered a reliable additional test for periprosthetic joint infection diagnosis in everyday clinical practice.
Hyper-scale analysis of surface roughness
Authors: Lindsay John B , Newman Daniel R
Published: August 2018

Surface roughness is frequently measured using DEMs to characterize the ruggedness and topographic complexity of landscapes. Roughness maps have been applied in geological mapping, ecological modeling, and other environmental applications. These maps are typically derived using a roving-window approach, where kernel size dictates the scale at which roughness is assessed. The pattern of roughness is strongly scale dependent and this roughness-scaling relation can reveal useful information about the geomorphologic character of landscapes. This study applied hyper-scale analysis of a normal-vector based roughness metric for a LiDAR DEM of Rondeau Bay, Canada. The use of integral images, a data structure for computationally efficient filtering operations, allowed for the fine scale resolution of the analysis. The unique roughness scale signature of each grid cell in the DEM was derived for all spatial scales ranging from 3 to 5000 cells (7.5 m to 12,502.5 m). Maps of maximum roughness and the scale of maximum roughness were created for the study site. This cell-specific scaling approach to the characterization of surface roughness is in contrast to the use of single, often arbitrarily selected, kernel sizes to map topographic attributes. The additional information provided by the scale map was found to provide valuable ancillary data for landscape interpretation.
Design and Simulation of Temperature Sensor based on Long Period Grating in Liquid Filled Photonic Crystal Fiber
Authors: Boufenar R. , Bouamar M. , Hocini A.
Published: August 2018

In this paper, a high sensitivity temperature sensor based on photonic crystal fiber long period grating (PCF-LPG) filled with ethanol is proposed and simulated by full vector finite element method. The relationship between the resonant wavelength shift, and the temperature was analyzed. The results show that the resonant wavelength of the ethanol filled photonic crystal fiber long period grating is proportional linearly with temperature and the highest  sensitivity of  was achieved, which is 90 times higher than that of conventional LPG temperature sensors.
SAR Evaluation of Metallic Loop-like Accessory Effect of Broadband Wearable Planar Monopole Textile Antenna
Authors: Zainal H. H. , Rahim H. A. , Soh P. J. , Lago H. , Rani K. N. A. , Zulkefli M. S. , Lee Y. S. , Yah N. F. N.
Published: August 2018

This paper presents the investigation influence of the common metallic loop like accessory on Specific Absorption Rate (SAR) averaged over 10g and 1 g tissue.The simulations were made by means CST Microwave Studio software at frequencies 2.45GHz and 2.6GHz. Numerical analysis conducted using broadband textile monopole antenna (TM) with variations of orientation and distance showed that the SAR value increased when the antenna horizontally polarized.This is up to 80% more than vertically polarized TM placed closest item to 2mm.
Statistical Moments and Scintillation Level of Scattered Electromagnetic Waves in the Magnetized plasma
Authors: Jandieri G. V. , Ishimaru A. , Rawat B. , Gavrilenko V. , Kharshiladze O.
Published: August 2018

Statistical characteristics of scattered ordinary and extraordinary electromagnetic waves in the magnetized plasma are considered using the smooth perturbation method. Diffraction effects and polarization coefficients are taken into account. Second order statistical moments of scattered radiation are obtained for arbitrary correlation function of electron density fluctuations. Broadening of the spatial power spectrum and displacement of its maximum, wave phase structure function and the angle-of-arrivals are obtained for three-dimensional spectral function containing anisotropic Gaussian and power-law spectral functions. Scintillation level of scattered radiation is analyzed for different parameters characterizing anisotropic plasma irregularities for the ionospheric F-region. The spectral widths (first and second moments) of the power spectrum and scintillation periods are calculated for “frozen-in” drifting elongated plasma irregularities using the experimental data.
Low‐temperature Raman spectroscopy reveals small chromophore distortion in primary photointermediate of proteorhodopsin
Authors: Fujisawa Tomotsumi , Abe Masahiro , Tamogami Jun , Kikukawa Takashi , Kamo Naoki , Unno Masashi
Published: August 2018

Proteorhodopsin (PR) is a microbial rhodopsin functioning as a light‐driven proton pump in aquatic bacteria. We performed low‐temperature Raman measurements of PR to obtain the structure of the primary photoproduct, the K intermediate (PRK). PRK showed the hydrogen‐out‐of‐plane modes that are much less intense than those of bacteriorhodopsin as the prototypical light‐driven proton pump from haloarchaea. The present results reveal the significantly relaxed chromophore structure in PRK, which can be coupled to the slow kinetics of the K intermediate. This structure suggests that PR transports protons using the small energy storage within the chromophore at the start of its photocycle.
Consequences of Cre‐mediated deletion of Ciz1 exon 5 in mice
Authors: Xiao Jianfeng , Khan Mohammad Moshahid , Vemula Satya , Tian Jun , LeDoux Mark S.
Published: August 2018

CIZ1 plays a role in DNA synthesis at the G1/S checkpoint. Ciz1 gene‐trap null mice manifest motor dysfunction, cell‐cycle abnormalities, and DNA damage. In contrast, it has previously been reported that mouse embryonic fibroblasts derived from presumed Ciz1 knock‐out mice (Ciz1tm1.1Homy/tm1.1Homy) generated by crossing Cre‐expressing mice with exon 5‐floxed mice (Ciz1tm1Homy/tm1Homy) do not exhibit evidence of enhanced DNA damage following γ‐irradiation or cell‐cycle defects. Here, we report that Ciz1tm1.1Homy/tm1.1Homy mice show loss of Ciz1 exon 5 but are neurologically normal and express abnormal transcripts (Ciz1ΔE5/ΔE5 mice) that are translated into one or more proteins of approximate wild‐type size. Therefore, Ciz1tm1.1Homy/tm1.1Homy mice (Ciz1ΔE5/ΔE5) lose residues encoded by exon 5 but may gain function from novel amino acid sequences.
Identification of novel GLI1 target genes and regulatory circuits in human cancer cells
Authors: Diao Yumei , Rahman Mohammed Ferdous‐Ur , Vyatkin Yuri , Azatyan Ani , St. Laurent Georges , Kapranov Philipp , Zaphiropoulos Peter G.
Published: August 2018

Hedgehog (HH) signaling is involved in many physiological processes, and pathway deregulation can result in a wide range of malignancies. Glioma‐associated oncogene 1 (GLI1) is a transcription factor and a terminal effector of the HH cascade. Despite its crucial role in tumorigenesis, our understanding of the GLI1 cellular targets is quite limited. In this study, we identified multiple new GLI1 target genes using a combination of different genomic surveys and then subjected them to in‐depth validation in human cancer cell lines. We were able to validate >90% of the new targets, which were enriched in functions involved in neurogenesis and regulation of transcription, in at least one type of follow‐up experiment. Strikingly, we found that RNA editing of GLI1 can modulate effects on the targets. Furthermore, one of the top targets, FOXS1, a gene encoding a transcription factor previously implicated in nervous system development, was shown to act in a negative feedback loop limiting the cellular effects of GLI1 in medulloblastoma and rhabdomyosarcoma cells. Moreover, FOXS1 is both highly expressed and positively correlated with GLI1 in medulloblastoma samples of the Sonic HH subgroup, further arguing for the existence of FOXS1/GLI1 interplay in human tumors. Consistently, high FOXS1 expression predicts longer relapse‐free survival in breast cancer. Overall, our findings open multiple new avenues in HH signaling pathway research and have potential for translational implications.
ABCA1 overexpression worsens colorectal cancer prognosis by facilitating tumour growth and caveolin‐1‐dependent invasiveness, and these effects can be ameliorated using the BET inhibitor apabetalone
Authors: Aguirre‐Portolés Cristina , Feliu Jaime , Reglero Guillermo , Ramírez de Molina Ana
Published: August 2018

At the time of diagnosis, 20% of patients with colorectal cancer present metastasis. Among individuals with primary lesions, 50% of them will develop distant tumours with time. Therefore, early diagnosis and prediction of aggressiveness is crucial for therapy design and disease prognosis. Tumoral cells must undergo significant changes in energy metabolism to meet increased structural and energetic demands for cell proliferation, and metabolic alterations are considered to be a hallmark of cancer. Here, we present the ATP‐binding cassette transporter (ABCA1), a regulator of cholesterol transport, as a new marker for invasion and colorectal cancer survival. ABCA1 is significantly overexpressed in patients at advanced stages of colorectal cancer, and its overexpression confers proliferative advantages together with caveolin‐1 dependent‐increased migratory and invasive capacities. Thus, intracellular cholesterol imbalances mediated by ABCA1 overexpression may contribute to primary tumour growth and dissemination to distant locations. Furthermore, we demonstrate here that increased levels of apolipoprotein A1 (APOA1), a protein involved in cholesterol efflux and high‐density lipoprotein constitution, in the extracellular compartment modulates expression of ABCA1 by regulating COX‐2, and compensate for ABCA1‐dependent excessive export of cholesterol. APOA1 emerges as a new therapeutic option to inhibit the promotion of colorectal cancer to metastasis by modulating intracellular cholesterol metabolism. Furthermore, we propose apabetalone, an orally available small molecule that is currently being evaluated in clinical trials for the treatment of atherosclerosis, as a new putative therapeutic option to prevent colorectal cancer progression by increasing APOA1 expression and regulating reverse transport of cholesterol.
The triheme cytochrome PpcF from Geobacter metallireducens exhibits distinct redox properties
Authors: Ferreira Marisa R. , Dantas Joana M. , Salgueiro Carlos A.
Published: August 2018

Electrogenic bacteria, such as Geobacter, can couple the oxidation of carbon sources to the reduction of extracellular electron acceptors; such acceptors include toxic and radioactive metals, as well as electrode surfaces, making Geobacter a suitable candidate for applied use in bioremediation and bioenergy generation. Geobacter metallireducens is more promising in this regard than the better studied Geobacter sulfurreducens, as it has more efficient Fe (III) reduction rates and can convert nitrate to ammonia. The operon responsible for nitrate reductase activity in G. metallireducens includes the gene encoding the cytochrome PpcF, which was proposed to exchange electrons with nitrate reductase. In the present work, we perform a biochemical and a biophysical characterization of PpcF. Spectroscopic techniques, including circular dichroism (CD), UV‐visible, and nuclear magnetic resonance (NMR), revealed that the cytochrome is very stable (Tm > 85 °C), contains three low‐spin hemes, and is diamagnetic (S = 0) and paramagnetic (S = 1/2) in the reduced and oxidized states, respectively. The NMR chemical shifts of the heme substituents were assigned and used to determine the heme core architecture of PpcF. Compared to the PpcA‐family from G. sulfurreducens, the spatial disposition of the hemes is conserved, but the functional properties are clearly distinct. In fact, potentiometric titrations monitored by UV‐visible absorption reveal that the reduction potential values of PpcF are significantly less negative (−56 and −64 mV, versus the normal hydrogen electrode at pH 7.0 and 8.0, respectively). NMR redox titrations showed that the order of oxidation of the hemes is IV‐I‐III, a feature not observed for G. sulfurreducens. The different redox properties displayed by PpcF, including the small redox‐Bohr effect and low reduction potential value of heme IV, were structurally rationalized and attributed to the lower number of positively charged residues located in the vicinity of heme IV. Overall, the redox features of PpcF suggest that biotechnological applications of G. metallireducens may require less negative working functional redox windows than those using by G. sulfurreducens.
Tf2O‐Promoted Trifluoromethythiolation of Various Arenes Using NaSO2CF3
Authors: Liu Jie , Zhao Xiaochun , Jiang Lvqi , Yi Wenbin
Published: August 2018

A sulfonic anhydride‐promoted direct trifluoromethylthiolation using NaSO2CF3 has been developed. The simple and practical strategy enabled the direct introduction of SCF3 moiety into unexplored arene scaffolds under reductant‐ and metal‐free condition at room temperature.

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SO42−/ZrO2 supported on γ‐Al2O3 as a catalyst for CO2 desorption from CO2‐loaded monoethanolamine solutions
Authors: Zhang Xiaowen , Hong Jieling , Liu Helei , Luo Xiao , Olson Wilfred , Tontiwachwuthikul Paitoon , Liang Zhiwu
Published: August 2018

In this work, the composite catalysts, SO42/ZrO2/γ‐Al2O3 (SZA), with different ZrO2 and γ‐Al2O3 mass ratios were prepared and used for the first time for the carbon dioxide (CO2)‐loaded monoethanolamine (MEA) solvent regeneration process to reduce the heat duty. The regeneration characteristics with five catalysts (three SZA catalysts and two parent catalysts) of a 5 M MEA solution with an initial CO2 loading of 0.5 mol CO2/mol amine at 98°C were investigated in terms of CO2 desorption performance and compared with those of a blank test. All the catalysts were characterized using X‐ray diffraction, Fourier transform infrared spectroscopy, N2 adsorption–desorption experiment, ammonia temperature programmed desorption, and pyridine‐adsorption infrared spectroscopy. The results indicate that the SZA catalysts exhibited superior catalytic activity to the parent catalysts. A possible catalytic mechanism for the CO2 desorption process over SZA catalyst was proposed. The results reveal that SZA1/1, which possesses the highest joint value of Brφnsted acid sites (BASs) and mesopore surface area (MSA), presented the highest catalytic performance, decreasing the heat duty by 36.9% as compared to the catalyst‐free run. The SZA1/1 catalyst shows the best catalytic performance as compared with the reported catalyst for this purpose. Moreover, the SZA catalyst has advantages of low cost, good cyclic stability, easy regeneration and has no effect on the CO2 absorption performance of MEA. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3988–4001, 2018
Sexual dimorphism in the ontogeny of second (2D) and fourth (4D) digit lengths, and digit ratio (2D:4D)
Authors: Manning John T. , Fink Bernhard
Published: August 2018

Objective

Sex differences are often reported in digit lengths and digit ratio (2D:4D). However, the ontogeny of these sex differences and their interrelationships are less well known.

Methods

We considered sex differences in the lengths of the 2nd (2D) and 4th (4D) digit and 2D:4D in children aged 2 to 18 years (Sample I, n = 680) and adults aged 18 to 30 years (Sample II, n = 89,246). Digit length was determined by direct experimenter‐measurement (Sample I) and direct self‐measurement (Sample II). The data were tested with two‐factor ANOVA's (sex and year‐group).

Results

In both samples, there were significant main effects of sex and year‐group, and a significant interaction effect on digit length. Digit length was positively related to age in both samples. Boys had longer digits than girls but only after 13 years. Men had longer digits than women and the dimorphism increased from 18 to 30 years. There were significant sex differences in 2D:4D (males < females), but no significant effect of age and no interaction effect of age and sex on 2D:4D in children or adults.

Conclusions

Between 2 and 30 years, the lengths and the sexual dimorphisms of 2D and 4D are dependent on age. In contrast, 2D:4D is not age‐dependent. We discuss our findings in the context of the ontogeny of digits and in the light of recent claims on the presence of static allometry in 2D and 4D lengths.
Tuning Gold Nanoparticles with Chelating Ligands for Highly Efficient Electrocatalytic CO2 Reduction
Authors: Cao Zhi , Zacate Samson B. , Sun Xiaodong , Liu Jinjia , Hale Elizabeth M. , Carson William P. , Tyndall Sam B. , Xu Jun , Liu Xingwu , Liu Xingchen , Song Chang , Luo Jheng‐hua , Cheng Mu‐Jeng , Wen Xiaodong , Liu Wei
Published: August 2018

Capped chelating organic molecules are presented as a design principle for tuning heterogeneous nanoparticles for electrochemical catalysis. Gold nanoparticles (AuNPs) functionalized with a chelating tetradentate porphyrin ligand show a 110‐fold enhancement compared to the oleylamine‐coated AuNP in current density for electrochemical reduction of CO2 to CO in water at an overpotential of 340 mV with Faradaic efficiencies (FEs) of 93 %. These catalysts also show excellent stability without deactivation (<5 % productivity loss) within 72 hours of electrolysis. DFT calculation results further confirm the chelation effect in stabilizing molecule/NP interface and tailoring catalytic activity. This general approach is thus anticipated to be complementary to current NP catalyst design approaches.
Intermetalloide Cluster: Moleküle und Festkörper im Dialog
Authors: Mayer Kerstin , Weßing Jana , Fässler Thomas F. , Fischer Roland A.
Published: August 2018

Atompräzise und ligandenstabilisierte metalloide Cluster haben sich als herausragende Modellsysteme für grundlegende Struktur‐ und Bindungssituationen in kompositionell verwandten Molekülen und Festkörperphasen erwiesen. Dieses faszinierende Forschungsfeld ist jedoch noch immer stark auf Systeme homometallischer und pseudo‐homometallischer verwandter d‐Block‐Metalle beschränkt. In diesem Aufsatz möchten wir unsere eigenen sowie die Leistungen anderer hervorheben, um die strukturelle und kompositionelle Vielfalt intermetallischer Phasen mit ungleichen d‐ und p‐Block‐Metallkombinationen auf molekularem Level darzustellen, im Besonderen anhand der Zintl‐ und Hume‐Rothery‐Phasen. Ziel ist es, die Kluft zwischen der heterometallischen molekularen Koordinationschemie und den Festkörperphasen zu überbrücken. Hierbei werden grundlegende synthetische Herangehensweisen sowie strukturelle und elektronische Eigenschaften solcher “molekularer Legierungen” angesprochen und ihre außergewöhnliche Position als Zwischenschritt auf dem Weg zu Nanomaterialien hervorgehoben.
Supramolekulare Metallopolymere: Von linearen Materialien zu infiniten Netzwerken
Authors: Bentz Kyle C. , Cohen Seth M.
Published: August 2018

Koordinationspolymere (coordination polymers, CPs) und supramolekulare Metallopolymere (supramolecular metallopolymers, SMPs) sind seit Jahrzehnten Gegenstand ausgiebiger Forschung. Spektakuläre Fortschritte in beiden Feldern haben neue Verbindungen hervorgebracht, die an der Grenze zwischen diesen beiden organisch‐anorganischen Gebieten liegen. An dieser Schnittstelle wurden Materialien entwickelt auf Basis unterschiedlicher Konzepte wie molekularem Flechten, supramolekularen Clustern und Hybriden aus Metall‐organischen Gerüstverbindungen und Polymeren. Dieser Kurzaufsatz gewährt einen Einblick in die intellektuelle Entstehung sowie die Verbindungen zwischen verschiedenen supramolekularen Konstrukten und den Stand der Wissenschaft bezüglich neuer Materialien an dieser Schnittstelle.
Supramolecular Assemblies with Near‐Infrared Emission Mediated in Two Stages by Cucurbituril and Amphiphilic Calixarene for Lysosome‐Targeted Cell Imaging
Authors: Chen Xu‐Man , Chen Yong , Yu Qilin , Gu Bo‐Han , Liu Yu
Published: August 2018

A two‐stage mediated near‐infrared (NIR) emissive supramolecular assembly for lysosome‐targeted cell imaging is presented. 4,4′‐Anthracene‐9,10‐diylbis(ethene‐2,1‐diyl))bis(1‐ethylpyridin‐1‐ium) bromide (ENDT) was synthesized as an organic dye with weak fluorescence emission at 625 nm. When ENDT complexes with cucurbit[8]uril (CB[8]), this binary supramolecular complex assembles into nanorods with a near‐infrared fluorescence emission (655 nm) and fluorescence enhancement as the first stage. Such supramolecular complexes interact with lower‐rim dodecyl‐modified sulfonatocalix[4]arene (SC4AD) to form nanoparticles for further fluorescence enhancement as the second stage. Furthermore, based on a co‐staining experiment with LysoTracker Blue, such nanoparticles can be applied in NIR lysosome‐targeted cell imaging.
A Carboxylate to Amide Substitution That Switches Protein Folds
Authors: Gianni Stefano , McCully Michelle E. , Malagrinò Francesca , Bonetti Daniela , De Simone Alfonso , Brunori Maurizio , Daggett Valerie
Published: August 2018

Metamorphic proteins are biomolecules prone to adopting alternative conformations. Because of this feature, they represent ideal systems to investigate the general rules allowing primary structure to dictate protein topology. A comparative molecular dynamics study was performed on the denatured states of two proteins, sharing nearly identical amino‐acid sequences (88 %) but different topologies, namely an all‐α‐helical bundle protein named GA88 and an α+β‐protein named GB88. The analysis allowed successful design of and experimental validation of a site‐directed mutant that promotes, at least in part, the switch in folding from GB88 to GA88. The mutated position, in which a glutamic acid was replaced by a glutamine, does not make any intramolecular interactions in the native state of GA88, such that its stabilization can be explained by considering the effects on the denatured state. The results represent a direct demonstration of the role of the denatured state in sculpting native structure.
Stereospecific β‐l‐Rhamnopyranosylation through an SNi‐Type Mechanism by Using Organoboron Reagents
Authors: Nishi Nobuya , Sueoka Kazuhiro , Iijima Kiyoko , Sawa Ryuichi , Takahashi Daisuke , Toshima Kazunobu
Published: August 2018

Stereospecific β‐l‐rhamnopyranosylations were conducted using a 1,2‐anhydro‐l‐rhamnopyranose donor and mono‐ol or diol acceptors in the presence of a glycosyl‐acceptor‐derived borinic or boronic ester. Reactions proceeded smoothly to provide the corresponding β‐l‐rhamnopyranosides (β‐l‐Rhap) with complete stereoselectivity in moderate to high yields without any further additives under mild conditions. Mechanistic studies of the borinic ester mediated glycosylation using 13C kinetic isotope effect (KIE) measurements and DFT calculations were consistent with a concerted SNi mechanism with an exploded transition state. In addition, the present glycosylation method was applied successfully to the synthesis of a trisaccharide, α‐l‐Rhap‐(1,2)‐β‐l‐Rhap‐(1,4)‐Glcp, derived from Streptococcus pneumoniae serotypes 7B, 7C, and 7D.
Photo‐Organocatalytic Enantioselective Radical Cascade Reactions of Unactivated Olefins
Authors: Bonilla Pablo , Rey Yannick P. , Holden Catherine M. , Melchiorre Paolo
Published: August 2018

Radical cascade processes are invaluable for their ability to rapidly construct complex chiral molecules from simple substrates. However, implementing catalytic asymmetric variants is difficult. Reported herein is a visible‐light‐mediated organocatalytic strategy that exploits the excited‐state reactivity of chiral iminium ions to trigger radical cascade reactions with high enantioselectivity. By combining two sequential radical‐based bond‐forming events, the method converts unactivated olefins and α,β‐unsaturated aldehydes into chiral adducts in a single step. The implementation of an asymmetric three‐component radical cascade further demonstrates the complexity‐generating power of this photochemical strategy.
Ammonia Storage by Reversible Host–Guest Site Exchange in a Robust Metal–Organic Framework
Authors: Godfrey Harry G. W. , da Silva Ivan , Briggs Lydia , Carter Joseph H. , Morris Christopher G. , Savage Mathew , Easun Timothy L. , Manuel Pascal , Murray Claire A. , Tang Chiu C. , Frogley Mark D. , Cinque Gianfelice , Yang Sihai , Schröder Martin
Published: August 2018

MFM‐300(Al) shows reversible uptake of NH3 (15.7 mmol g−1 at 273 K and 1.0 bar) over 50 cycles with an exceptional packing density of 0.62 g cm−3 at 293 K. In situ neutron powder diffraction and synchrotron FTIR micro‐spectroscopy on ND3@MFM‐300(Al) confirms reversible H/D site exchange between the adsorbent and adsorbate, representing a new type of adsorption interaction.
Einstellbare orthogonale reversible kovalente Bindungen: dynamische Kontrolle über die molekulare Selbstorganisation
Authors: Reuther James F. , Dahlhauser Samuel D. , Anslyn Eric V.
Published: August 2018

Die dynamische Selbstorganisation von Makromolekülen in biologischen Systemen ist ein Grundprozess des Lebens und beruht herkömmlicherweise auf nichtkovalenten Wechselwirkungen. Allerdings bieten dynamische Gleichgewichte mit reversiblen kovalenten Bindungen eine vielversprechende Option zum Design von Funktionsmaterialien, zum Bottom‐up‐Aufbau und für molekulare Maschinen. In diesem Kurzaufsatz werden aktuelle Fortschritte und Anwendungen im Bereich der einstellbaren orthogonalen reversiblen kovalenten Bindungen (Tunable Orthogonal Reversible Covalent (TORC) bonds) in den genannten Bereichen dargelegt, und es wird ein Ausblick auf zukünftige Entwicklungsmöglichkeiten, besonders bei synthetisch codierten Polynukleotidmimetika, gegeben.
Intermetalloid Clusters: Molecules and Solids in a Dialogue
Authors: Mayer Kerstin , Weßing Jana , Fässler Thomas F. , Fischer Roland A.
Published: August 2018

Atom‐precise, ligand‐stabilized metalloid clusters have emerged as outstanding model systems to study fundamental structure and bonding situations of compositionally related molecules and extended solid phases. However, this fascinating field of research is still largely restricted to homometallic and pseudo‐heterometallic systems of closely related d‐block metals. In this review, we will highlight our own and others’ efforts to project the structural and compositional diversity of intermetallics with dissimilar d‐ and p‐block metal combinations, particularly the Zintl and Hume‐Rothery phases, onto the molecular level in order to bridge the still gaping chasm between heterometallic molecular coordination chemistry and solid‐state intermetallics. Herein, fundamental synthetic approaches, as well as structural and electronic properties of thus accessible “molecular alloys” will be addressed, and placed against their exceptional position as intermediates on the way to nanomaterials.
Supramolecular Metallopolymers: From Linear Materials to Infinite Networks
Authors: Bentz Kyle C. , Cohen Seth M.
Published: August 2018

The fields of coordination polymers (CPs) and supramolecular metallopolymers (SMPs) have been extensively studied for decades. Spectacular recent advances in both fields have created new compounds that lie at the interface between these two classes of organic‐inorganic hybrid materials. At this interface, materials based on molecular weaving, supramolecular clusters, and metal‐organic framework‐polymer hybrids have emerged. This minireview provides a perspective on the intellectual emergence and connection between different supramolecular constructs and the state of the art with respect to this new materials interface.
Tunable Orthogonal Reversible Covalent (TORC) Bonds: Dynamic Chemical Control over Molecular Assembly
Authors: Reuther James F. , Dahlhauser Samuel D. , Anslyn Eric V.
Published: August 2018

Dynamic assembly of macromolecules in biological systems is one of the fundamental processes that facilitates life. Although such assembly most commonly uses noncovalent interactions, a set of dynamic reactions involving reversible covalent bonding is actively being exploited for the design of functional materials, bottom‐up assembly, and molecular machines. This Minireview highlights recent implementations and advancements in the area of tunable orthogonal reversible covalent (TORC) bonds for these purposes, and provides an outlook for their expansion, including the development of synthetically encoded polynucleotide mimics.
Lyotropic Chromonic Mesophases Derived from Metal–Organic Complexes
Authors: Gao Qin , Zou Chao , Lu Wei
Published: August 2018

Lyotropic chromonic (LC) mesophases have received a large amount of attention, owing to the semi‐stable nature of the chromonics. In these systems, the balance between the ordering forces and the thermal motion is delicate. As such, temperature changes, concentration variations, alterations to the electric and magnetic fields, and the addition of additives to the chromonic systems can be sensitively monitored. Herein, we review the general characterization methods for lyotropic chromonic mesophases, including polarized optical microscopy (POM), multinuclear NMR spectroscopy, X‐ray diffractometry, cryo‐TEM, and rheology. In recent years, lyotropic chromonic mesophases that are derived from metal–organic complexes have become established and offer the possibility of introducing the rich functionalities of the metal complexes into these systems. The chromonic properties, aggregation behaviors, and influence factors on such systems are reviewed case‐by‐case. Finally, preliminary attempts to utilize these systems are reviewed, which have demonstrated their potential application in optical devices, biosensing, luminescent materials, etc.
Triamterene‐Grafted Graphitic Carbon Nitride with Electronic Potential Redistribution for Efficient Photocatalytic Hydrogen Evolution
Authors: Sun Miao , Li Kui , Zhang Wei‐De , Yu Yu‐Xiang
Published: August 2018

In this study, a photocatalyst with a distorted skeleton and synthesized by grafting triamterene onto graphitic carbon nitride (g‐C3N4) frameworks was prepared. The pteridine ring of the triamterene‐based nitrogen‐enriched organic structure functions as a trapped electron site owing to its inductive effect. The benzene ring in triamterene plays an important role in the even dispersion of electrons by a conjugative effect. Redistribution of the intramolecular electronic potential is caused by a synergistic effect between the pteridine and benzene rings of triamterene and promotes separation and migration of the photoinduced charge carriers. After coupling with triamterene, the π electrons of g‐C3N4 are relocated; that is, the intrinsic electronic and band structures of g‐C3N4 are effectively modulated. The modified polymeric photocatalyst shows a high photocatalytic H2 evolution rate of 157.5 μmol h−1, a value that is 4.3 times higher than the H2 evolution rate of pristine g‐C3N4 (36.8 μmol h−1), with an apparent quantum efficiency of 9.7 % at λ=450 nm. The incorporation of triamterene into the g‐C3N4 frameworks significantly expands its π‐delocalized system by redistribution of the electronic potential, expands the visible‐light absorption range, and effectively promotes the separation and migration of photoinduced charge carriers. This strategy may provide a reference for promoting charge separation of g‐C3N4 through redistribution of the electronic potential and for synthesizing novel carbon nitride based semiconductors for efficient solar energy conversion into hydrogen.
Metabolism of steroids by cytochrome P450 2C9 variants
Authors: Uno Tomohide , Nakano Ryosuke , Kitagawa Risa , Okada Mai , Kanamaru Kengo , Takenaka Shinji , Uno Yuichi , Imaishi Hiromasa
Published: August 2018

CYP2C9 is a human microsomal cytochrome P450c (CYP). Much variation in CYP2C9 levels and activity can be attributed to polymorphisms of this gene. Wild‐type CYP2C9 and ten mutants were co‐expressed with NADPH‐cytochrome P450 reductase in Escherichia coli. The hydroxylase activities toward steroids were examined. CYP2C9.2, CYP2C9.3, CYP2C9.4, CYP2C9.16, CYP2C9.28, CYP2C9.48 and CYP2C9.52 had higher testosterone 6β‐hydroxylation than CYP2C9.1. CYP2C9.4 showed higher progesterone 6β‐hydroxylation activity than CYP2C9.1. CYP2C9.28 and CYP2C9.48 showed higher progesterone 11α‐hydroxylation activity than CYP2C9.1. CYP2C9.48 showed higher progesterone 16α‐hydroxylation activity than CYP2C9.1. CYP2C9.2, CYP2C9.3, CYP2C9.16 and CYP2C9.30 had higher estrone 16α‐hydroxylation activity than CYP2C9.1. CYP2C9.3 had higher estrone 11α‐hydroxylation activity than CYP2C9.1. CYP2C9.39 and CYP2C9.57 showed similar activities to CYP2C9.1. These results indicate that the substrate specificity of CYP2C9.39 and CYP2C9.57 was not changed, but CYP2C9.2, CYP2C9.3, CYP2C9.4, CYP2C9.16, CYP2C9.28, CYP2C9.30, CYP2C9.48 and CYP2C9.52 showed different hydroxylation activities toward steroids compared with CYP2C9.1.
Porous Organic Polymers for CO2 Storage and Conversion Reactions
Authors: Bhanja Piyali , Modak Arindam , Bhaumik Asim
Published: August 2018

To overcome the challenges of global warming and environmental pollution it is mandatory to reduce the concentration of atmospheric carbon dioxide (CO2), which is largely accumulated in air through the combustion of fossil fuels. Thus, sequestration of CO2 through physisorption on solid adsorbents and their successful conversion into value added fine chemicals are the major priority areas of research today. Innovation of efficient solid CO2‐philic adsorbents together with their high mechanical/chemical stability and regeneration efficiency are the most challenging objectives to achieve this goal. In this context, porous organic polymers (POPs) owing to their high specific surface area, chemical stability, nanoscale porosity and structural diversity have huge potential to play as selective CO2 adsorbent. POPs synthesized through large varieties of reactive monomers via simple and convenient chemical routes can be the ideal adsorbents for the CO2 storage and fixation reactions. A wide range of POPs can be synthesized from different multidentate amines, aldehydes, carboxylic acids or triazine monomers through the polycondensation reactions or solid state condensation reactions. Ease of synthesis, uniform pore width together with high surface area and surface basic sites (nitrogen and other heteroelements) play crucial role in the CO2 absorption and conversion reactions. This review provides a concise account in designing POPs and their application in CO2 adsorption and fixation into reactive organic molecules for the synthesis of fuels and value added fine chemicals.
Staple‐Based Paper Electrochemical Platform for Celiac Disease Diagnosis
Authors: Nanni Paula I. , González‐López Andrea , Nunez‐Bajo Estefanía , Madrid Rossana E. , Fernández‐Abedul M. T.
Published: August 2018

A staple‐based electrochemical platform is proposed for the first time as a simple and low‐cost detection system for paper‐based devices. The system, which incorporates small and disposable stainless‐steel staples as electrodes, is combined with a paper strip. The staple acting as the working electrode is modified with carbon ink. The platform was carefully optimized with ferrocene carboxylic acid. As a proof‐of‐concept, it was employed for the enzymatic [horseradish peroxidase (HRP)‐based] immunoelectroanalytical detection of human tissue anti‐transglutaminase (anti‐tTG), which is a biomarker for celiac disease diagnosis. The intensity of the current from the electrochemical reduction of 3,3′,5,5′‐tetramethylbenzidine (an HRP substrate) was recorded chronoamperometrically at −0.2 V in different paper areas. A linear relationship between the current measured at 30 s and the logarithm of the concentration of anti‐tTG in the range comprised between 3 and 100 U mL−1 was obtained. Negative and positive controls produced expected values. Results demonstrated that the paper/staple combined platform is very convenient for the detection of electroactive analytes and other compounds that can be determined indirectly in bioassays.
The Coming of Age in Iodane‐Guided ortho‐C−H Propargylation: From Insight to Synthetic Potential
Authors: Izquierdo Susana , Bouvet Sébastien , Wu Yichen , Molina Sonia , Shafir Alexandr
Published: August 2018

As early as 1991 Ochiai et al. reported that an acid‐activated form of phenyliodine diacetate, PhI(OAc)2, undergoes a reaction with propargyl‐silanes, germanes and stannanes to give the ortho‐propargyl iodobenzene. This formal C−H alkylation was proposed to take place through an unusual (even to date) iodonio‐based [3,3] rearrangement of an intermediate allenylsilane. Although this mechanistic principle has been invoked in related iodane‐directed C−H coupling reaction, some underlying principles have remained unaddressed, and the reaction rarely employed. Herein, DFT evidence for a mechanism best described as iodine‐guided electrophilic aromatic substitution is presented. Using a newly optimized reaction protocol that significantly reduces the undesired reduction process, the potency of the method is showcased through the synthesis of >40 structurally diverse ortho‐iodo propargyl (or allenyl) arenes.
3‐Mono‐Substituted BINOL Phosphoric Acids as Effective Organocatalysts in Direct Enantioselective Friedel–Crafts‐Type Alkylation of N‐Unprotected α‐Ketiminoester
Authors: Yonesaki Ryohei , Kondo Yuta , Akkad Walaa , Sawa Masanao , Morisaki Kazuhiro , Morimoto Hiroyuki , Ohshima Takashi
Published: August 2018

Although BINOL‐derived phosphoric acids are among the most widely used chiral Brønsted acid organocatalysts, their structures are mostly limited to 3,3′‐disubstituted ones and simple 3‐mono‐substituted ones without any polar functionalities on the 3‐substituent have not been used in highly enantioselective reactions. This work reports such 3‐mono‐substituted analogues as effective organocatalysts in direct highly enantioselective Friedel–Crafts‐type alkylation of N‐unprotected α‐ketiminoester. The origin of the observed high enantioselectivity with the 3‐mono‐substituted catalyst is also discussed.
Association of Healthcare Plan with atrial fibrillation prescription patterns
Authors: Chang Andrew Young , Askari Mariam , Fan Jun , Heidenreich Paul A. , Michael Ho P. , Mahaffey Kenneth W. , Ullal Aditya Jathin , Perino Alexander Carroll , Turakhia Mintu P.
Published: August 2018

Background

Atrial fibrillation (AF) is treated by many types of physician specialists, including primary care physicians (PCPs). Health plans have different policies for how patients encounter these providers, and these may affect selection of AF treatment strategy.

Hypothesis

We hypothesized that healthcare plans with PCP‐gatekeeping to specialist access may be associated with different pharmacologic treatments for AF.

Methods

We performed a retrospective cohort study using a commercial pharmaceutical claims database. We utilized logistic regression models to compare odds of prescription of oral anticoagulant (OAC), non‐vitamin K‐dependent oral anticoagulant (NOAC), rate control, and rhythm control medications used to treat AF between patients with PCP‐gated healthcare plans (eg, HMO, EPO, POS) and patients with non‐PCP‐gated healthcare plans (eg, PPO, CHDP, HDHP, comprehensive) between 2007 and 2012. We also calculated median time to receipt of therapy within 90 days of index AF diagnosis.

Results

We found similar odds of OAC prescription at 90 days following new AF diagnosis in patients with PCP‐gated plans compared to those with non‐PCP‐gated plans (OR: OAC 1.01, P = 0.84; warfarin 1.05, P = 0.08). Relative odds were similar for rate control (1.17, P < 0.01) and rhythm control agents (0.93, P = 0.03). However, PCP‐gated plan patients had slightly lower likelihood of being prescribed NOACs (0.82, P = 0.001) than non‐gated plan patients. Elapsed time until receipt of medication was similar between PCP‐gated and non‐gated groups across drug classes.

Conclusions

Pharmaceutical claims data do not suggest that PCP‐gatekeeping by healthcare plans is a structural barrier to AF therapy, although it was associated with lower use of NOACs.
Use of ticagrelor alongside fibrinolytic therapy in patients with ST‐segment elevation myocardial infarction: Practical perspectives based on data from the TREAT study
Authors: Berwanger Otavio , Abdelhamid Magdy , Alexander Thomas , Alzubaidi Abdulmajeed , Averkov Oleg , Aylward Philip , Contreras Zúñiga Eduardo , Halvorsen Sigrun , Iglesias Ricardo , A. SK. Abdul Kader Muhamad , Zubaid Mohammad , AlHabib Khalid F.
Published: August 2018

Primary percutaneous coronary intervention (PCI) is the preferred reperfusion method in patients with ST‐segment elevation myocardial infarction (STEMI). In patients with STEMI who cannot undergo timely primary PCI, pharmacoinvasive treatment is recommended, comprising immediate fibrinolytic therapy with subsequent coronary angiography and rescue PCI if needed. Improving clinical outcomes following fibrinolysis remains of great importance for the many patients globally for whom rapid treatment with primary PCI is not possible. For patients with acute coronary syndrome who underwent primary PCI, the PLATO trial demonstrated superior efficacy of ticagrelor relative to clopidogrel. Results in the predefined subgroup of patients with STEMI were consistent with the overall PLATO trial. Patients who received fibrinolytic therapy in the 24 hours before randomization were excluded from PLATO, and there is thus a lack of data on the safety of using ticagrelor in conjunction with fibrinolytic therapy in the first 24 hours after STEMI. The TREAT study addresses this knowledge gap; patients with STEMI who had symptom onset within the previous 24 hours and had received fibrinolytic therapy (of whom 89.4% had also received clopidogrel) were randomized to treatment with ticagrelor or clopidogrel (median time between fibrinolysis and randomization: 11.5 hours). At 30 days, ticagrelor was found to be non‐inferior to clopidogrel for the primary safety outcome of Thrombolysis in Myocardial Infarction (TIMI)‐defined first major bleeding. Considering together the results of the PLATO and TREAT studies, initiating or switching to treatment with ticagrelor within the first 24 hours after STEMI in patients receiving fibrinolysis is reasonable.
Synthesis and Biological in vitro and in vivo Evaluation of 2‐(5‐Nitroindazol‐1‐yl)ethylamines and Related Compounds as Potential Therapeutic Alternatives for Chagas Disease
Authors: Martín‐Escolano Rubén , Aguilera‐Venegas Benjamín , Marín Clotilde , Martín‐Montes Álvaro , Martín‐Escolano Javier , Medina‐Carmona Encarnación , Arán Vicente J. , Sánchez‐Moreno Manuel
Published: August 2018

Chagas disease, a neglected tropical disease caused by infection with the protozoan parasite Trypanosoma cruzi, is a potentially life‐threatening illness that affects 5–8 million people in Latin America, and more than 10 million people worldwide. It is characterized by an acute phase, which is partly resolved by the immune system, but then develops as a chronic disease without an effective treatment. There is an urgent need for new antiprotozoal agents, as the current standard therapeutic options based on benznidazole and nifurtimox are characterized by limited efficacy, toxicity, and frequent failures in treatment. In vitro and in vivo assays were used to identify some new low‐cost 5‐nitroindazoles as a potential antichagasic therapeutic alternative. Compound 16 (3‐benzyloxy‐5‐nitro‐1‐vinyl‐1H‐indazole) showed improved efficiency and lower toxicity than benznidazole in both in vitro and in vivo experiments, and its trypanocidal activity seems to be related to its effect at the mitochondrial level. Therefore, compound 16 is a promising candidate for the development of a new anti‐Chagas agent, and further preclinical evaluation should be considered.