bluuebunny/crossref_metadata_2025 huggingface dataset:
Patients With Early‐Onset Gout and Development of Earlier Severe Joint Involvement and Metabolic Comorbid Conditions: Results From a Cross‐Sectional Epidemiologic Survey
Authors: Pascart Tristan , Norberciak Laurène , Ea Hang‐Korng , Guggenbuhl Pascal , Lioté Frédéric
Published: July 2018

Objective

Little is known of the clinical features and comorbidity profile of patients presenting with early‐onset gout (EOG), although international guidelines recommend rapid treatment after diagnosis. The objective of this study was to assess specific characteristics and comorbidities of patients with gout who had an early onset.

Methods

Patients from a cross‐sectional French national cohort who experienced their first gout flare before age 40 years were included in the EOG group and compared to patients with an onset after age 40 years, the common gout group.

Results

A total of 120 patients were included in the EOG group (mean ± SD age 49.5 ± 11.9 years) and 865 patients in the common gout group (mean ± SD age 64.4 ± 10.1 years). Patients with EOG more often presented with a history of polyarticular flares (P < 0.01), but had similar frequency of flares (P = 0.16), gout arthropathy (P = 0.79), and tophi (P = 0.53). Prevalence of each item comprising metabolic syndrome did not differ between groups. In patients with EOG, all cardiovascular comorbidities were diagnosed after gout onset. Greater age, low high‐density lipoprotein, and excessive alcohol intake were associated in multivariate analysis with the common gout group, while a familial history of gout, longer duration of urate‐lowering treatment, higher serum uric acid levels, and metabolic syndrome were associated with the EOG group.

Conclusion

Patients with EOG developed slightly more severe joint involvement and earlier metabolic disorders than patients with common gout.
Active Materials for Organic Electrochemical Transistors
Authors: Zeglio Erica , Inganäs Olle
Published: July 2018

The organic electrochemical transistor (OECT) is a device capable of simultaneously controlling the flow of electronic and ionic currents. This unique feature renders the OECT the perfect technology to interface man‐made electronics, where signals are conveyed by electrons, with the world of the living, where information exchange relies on chemical signals. The function of the OECT is controlled by the properties of its core component, an organic conductor. Its chemical structure and interactions with electrolyte molecules at the nanoscale play a key role in regulating OECT operation and performance. Herein, the latest research progress in the design of active materials for OECTs is reviewed. Particular focus is given on the conducting polymers whose properties lead to advances in understanding the OECT working mechanism and improving the interface with biological systems for bioelectronics. The methods and device models that are developed to elucidate key relations between the structure of conducting polymer films and OECT function are discussed. Finally, the requirements of OECT design for in vivo applications are briefly outlined. The outcomes represent an important step toward the integration of organic electronic components with biological systems to record and modulate their functions.
High‐Mobility Helical Tellurium Field‐Effect Transistors Enabled by Transfer‐Free, Low‐Temperature Direct Growth
Authors: Zhou Guanyu , Addou Rafik , Wang Qingxiao , Honari Shahin , Cormier Christopher R. , Cheng Lanxia , Yue Ruoyu , Smyth Christopher M. , Laturia Akash , Kim Jiyoung , Vandenberghe William G. , Kim Moon J. , Wallace Robert M. , Hinkle Christopher L.
Published: July 2018

The transfer‐free direct growth of high‐performance materials and devices can enable transformative new technologies. Here, room‐temperature field‐effect hole mobilities as high as 707 cm2 V−1 s−1 are reported, achieved using transfer‐free, low‐temperature (≤120 °C) direct growth of helical tellurium (Te) nanostructure devices on SiO2/Si. The Te nanostructures exhibit significantly higher device performance than other low‐temperature grown semiconductors, and it is demonstrated that through careful control of the growth process, high‐performance Te can be grown on other technologically relevant substrates including flexible plastics like polyethylene terephthalate and graphene in addition to amorphous oxides like SiO2/Si and HfO2. The morphology of the Te films can be tailored by the growth temperature, and different carrier scattering mechanisms are identified for films with different morphologies. The transfer‐free direct growth of high‐mobility Te devices can enable major technological breakthroughs, as the low‐temperature growth and fabrication is compatible with the severe thermal budget constraints of emerging applications. For example, vertical integration of novel devices atop a silicon complementary metal oxide semiconductor platform (thermal budget <450 °C) has been theoretically shown to provide a 10× systems level performance improvement, while flexible and wearable electronics (thermal budget <200 °C) can revolutionize defense and medical applications.
Facile Assembly of a Large‐Area BNNSs Film for Oxidation/Corrosion‐Resistant Coatings
Authors: Teng Chao , Lin Yucai , Tan Yanli , Liu Jian , Wang Lei
Published: July 2018

Copper is one of the most widely used materials in industrial applications, such as electric power, electronics, and mechanical engineering fields. However, under high humidity, high temperature environment, acid, base, and salt solutions, the copper is vulnerable to destruction, which induces the oxidation and corrosion of copper surface. For circumventing these problems, a robust hydrophobic hexagonal boron nitride nanosheets (BNNSs) coating is facilely prepared through integrating the methods of liquid exfoliation, interface self‐assembly, and physics vapor deposition. The coating can prevent the copper to be oxidized at temperature as high as 500 °C. The corrosive droplets on the coating surface keep in Cassie's state and cannot penetrate into the valley of the topography, which effectively prevents the electrochemical corrosion at the interface between copper and the coating materials even under the DC voltage of 10 V. This finding sheds light on large‐scale constructing of oxidation/corrosion‐resistant coating for copper base materials toward practical industrial application.
High‐Performance Protonic Ceramic Fuel Cells with 1 µm Thick Y:Ba(Ce, Zr)O3 Electrolytes
Authors: Bae Kiho , Kim Dong Hwan , Choi Hyung Jong , Son Ji‐Won , Shim Joon Hyung
Published: July 2018

This study demonstrates the effectiveness of using thin‐film electrolytes to enhance protonic ceramic fuel cells (PCFCs). The material tested in this study is yttrium‐doped barium cerate‐zirconate (BCZY), which is a representative electrolyte material of PCFCs. The thickness of the electrolyte membrane is as small as 1 µm and designed to minimize ohmic loss in proton transport pathways. Integration of this thin BCZY electrolyte is attempted on a multilayered anode comprised of two‐step supports with bulk nickel‐yttria stabilized zirconia cermet as a base and thin nickel‐BCZY as an anode functional layer atop the base. The compatibility of this support with the deposited thin electrolyte is able to be confirmed from the results of iterated tests. The power of the fabricated cell is greater than 1.1 W cm−2 at 600 °C, which is a record high for PCFCs and is reproducible. In this paper, the origin of this high power is discussed and improvements that could be made to cell performance are further suggested.
Ultrastable In‐Plane 1T–2H MoS2 Heterostructures for Enhanced Hydrogen Evolution Reaction
Authors: Wang Shuai , Zhang Di , Li Bin , Zhang Chao , Du Zhiguo , Yin Haoming , Bi Xiaofang , Yang Shubin
Published: July 2018

Metallic 1T MoS2 is highly desirable for catalyzing electrochemical hydrogen production from water owing to its high electrical conductivity. However, stable 1T MoS2 is difficult to be produced in large‐scale by either common chemical or physical approaches. Here, ultrastable in‐plane 1T–2H MoS2 heterostructures are achieved via a simple one‐pot annealing treatment of 2H MoS2 bulk under a mixture gas of Ar and phosphorous vapor, where phosphorus cannot only occupy the interspace of MoS2 bulk, resulting in the expansion of MoS2, but also embed into the lattice of MoS2, inducing the partial phase transition from 2H to 1T phases of MoS2. Benefiting from its significantly improved electrical conductivity, highly exposed active sites, and hydrophily property, in‐plane 1T–2H MoS2 heterostructures exhibit largely improved electrocatalytic properties for hydrogen evolution reaction (HER) in alkaline electrolytes.
Three‐dimensional numerical simulation of upflow bubbling fluidized bed in opaque tube under high flux solar heating
Authors: Benoit Hadrien , Ansart Renaud , Neau Hervé , Garcia Triñanes Pablo , Flamant Gilles , Simonin Olivier
Published: July 2018

Solid particles can be used as a heat transfer medium in concentrated solar power plants to operate at higher temperature and achieve higher heat conversion efficiency than using the current solar heat transfer fluids that only work below 600°C. Among various particle circulation concepts, the dense particle suspension (DPS) flow in tubes, also called upflow bubbling fluidized bed (UBFB), was studied in the frame of the CSP2 FP7 European project. The DPS capacity to extract heat from a tube absorber exposed to concentrated solar radiation was demonstrated and the first values of the tube wall‐to‐DPS heat transfer coefficient were measured. A stable outlet temperature of 750°C was reached with a metallic tube, and a particle reflux in the near tube wall region was evidenced. In this article, the UBFB behavior is studied using the multiphase flow code NEPTUNE_CFD. Hydrodynamics of SiC Geldart A‐type particles and heat transfer imposed by a thermal flux at the wall are coupled in two‐dimensional unsteady numerical simulations. The convective/diffusive heat transfer between the gas and dispersed phase, and the inter‐particle radiative transfer (Rosseland approximation) are accounted for. Simulations and experiments are compared here and the temperature influence on the DPS flow is analyzed. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3857–3867, 2018
cPCET versus HAT: A Direct Theoretical Method for Distinguishing X–H Bond‐Activation Mechanisms
Authors: Klein Johannes E. M. N. , Knizia Gerald
Published: July 2018

Proton‐coupled electron transfer (PCET) events play a key role in countless chemical transformations, but they come in many physical variants which are hard to distinguish experimentally. While present theoretical approaches to treat these events are mostly based on physical rate coefficient models of various complexity, it is now argued that it is both feasible and fruitful to directly analyze the electronic N‐electron wavefunctions of these processes along their intrinsic reaction coordinate (IRC). In particular, for model systems of lipoxygenase and the high‐valent oxoiron(IV) intermediate TauD‐J it is shown that by invoking the intrinsic bond orbital (IBO) representation of the wavefunction, the common boundary cases of hydrogen atom transfer (HAT) and concerted PCET (cPCET) can be directly and unambiguously distinguished in a straightforward manner.
Kohlenstoffnitridmaterialien für photochemische Zellen zur Wasserspaltung
Authors: Volokh Michael , Peng Guiming , Barrio Jesús , Shalom Menny
Published: July 2018

Graphitische Kohlenstoffnitridmaterialien (CN) sind aufgrund ihrer einstellbaren Bandlücke, geeigneten Energiebandposition, hohen Stabilität unter harschen chemischen Bedingungen und geringen Kosten interessante Photokatalysatoren und heterogene Katalysatoren für zahlreiche Reaktionen. Allerdings befindet sich die Nutzung von CN in photoelektrochemischen (PEC) und photoelektronischen Bauelementen noch in einem frühen Stadium, da die Abscheidung einer hochwertigen und homogenen CN‐Schicht auf Substraten, die breite Bandlücke, die schlechte Ladungstrennungseffizienz sowie die geringe elektronische Leitfähigkeit noch Schwierigkeiten bereiten. In diesem Kurzaufsatz diskutieren wir Synthesewege zur Herstellung verschiedener Strukturen von CN auf Substraten und deren grundlegende photophysikalische Eigenschaften und photoelektrochemische Aktivität. Wir beschreiben die wesentlichsten Herausforderungen bei der Einbindung von CN in PEC‐Zellen sowie mögliche Wege zur Überwindung der bestehenden Beschränkungen zur Integration von CN‐Materialien in PEC und andere photoelektronische Bauelemente.
A Stable Crystalline Copper(I)–N2O Complex Stabilized as the Salt of a Weakly Coordinating Anion
Authors: Zhuravlev Vadim , Malinowski Przemysław J.
Published: July 2018

Nitrous oxide is considered a poor ligand, and therefore only a handful of well‐defined metal–N2O complexes are known. Oxidation of copper powder with an extreme oxidant, [Ag2I2][An]2 ([An]−=[Al(OC(CF3)3)4]−) in perfluorinated hexane leads to CuI[An], the first auxiliary ligand‐free CuI salt of the perfluorinated alkoxyaluminate anion. The compound is capable of forming a stable and crystalline complex with nitrous oxide, Cu(N2O)[An], where the Cu−N2O bond is by far the strongest among all other molecular metal–N2O complexes known. Thorough characterization of the compounds together with the crystal structure of Cu(N2O)[An] complex supported with DFT calculations are presented. These give insight into the bonding in the Cu+–N2O system and confirm N‐end coordination of the ligand.
Rational Design of MOF/COF Hybrid Materials for Photocatalytic H2 Evolution in the Presence of Sacrificial Electron Donors
Authors: Zhang Feng‐Ming , Sheng Jing‐Li , Yang Zhao‐Di , Sun Xiao‐Jun , Tang Hong‐Liang , Lu Meng , Dong Hong , Shen Feng‐Cui , Liu Jiang , Lan Ya‐Qian
Published: July 2018

Crystalline and porous covalent organic frameworks (COFs) and metal‐organic frameworks (MOFs) materials have attracted enormous attention in the field of photocatalytic H2 evolution due to their long‐range order structures, large surface areas, outstanding visible light absorbance, and tunable band gaps. In this work, we successfully integrated two‐dimensional (2D) COF with stable MOF. By covalently anchoring NH2‐UiO‐66 onto the surface of TpPa‐1‐COF, a new type of MOF/COF hybrid materials with high surface area, porous framework, and high crystallinity was synthesized. The resulting hierarchical porous hybrid materials show efficient photocatalytic H2 evolution under visible light irradiation. Especially, NH2‐UiO‐66/TpPa‐1‐COF (4:6) exhibits the maximum photocatalytic H2 evolution rate of 23.41 mmol g−1 h−1 (with the TOF of 402.36 h−1), which is approximately 20 times higher than that of the parent TpPa‐1‐COF and the best performance photocatalyst for H2 evolution among various MOF‐ and COF‐based photocatalysts.
An Environmentally Friendly and Flexible Aqueous Zinc Battery Using an Organic Cathode
Authors: Guo Zhaowei , Ma Yuanyuan , Dong Xiaoli , Huang Jianhang , Wang Yonggang , Xia Yongyao
Published: July 2018

Rechargeable batteries have been used to power various electric devices and store energy from renewables, but their toxic components (namely, electrode materials, electrolyte, and separator) generally cause serious environment issues when disused. Such toxicity characteristic makes them difficult to power future wearable electronic devices. Now an environmentally friendly and highly safe rechargeable battery, based on a pyrene‐4,5,9,10‐tetraone (PTO) cathode and zinc anode in mild aqueous electrolyte is presented. The PTO‐cathode shows a high specific capacity (336 mAh g−1) for Zn2+ storage with fast kinetics and high reversibility. Thus, the PTO//Zn full cell exhibits a high energy density (186.7 Wh kg−1), supercapacitor‐like power behavior and long‐term lifespan (over 1000 cycles). Moreover, a belt‐shaped PTO//Zn battery with robust mechanical durability and remarkable flexibility is first fabricated to clarify its potential application in wearable electronic devices.
Leveraging γ‐Glutamyl Transferase To Direct Cytotoxicity of Copper Dithiocarbamates against Prostate Cancer Cells
Authors: Bakthavatsalam Subha , Sleeper Mark L. , Dharani Azim , George Daniel J. , Zhang Tian , Franz Katherine J.
Published: July 2018

A prodrug approach is presented to direct copper‐dependent cytotoxicity to prostate cancer cells. The prochelator GGTDTC requires activation by γ‐glutamyl transferase (GGT) to release the metal chelator diethyldithiocarbamate from a linker that masks its thiol reactivity and metal binding properties. In vitro studies demonstrated successful masking of copper binding as well as clean liberation of the chelator by GGT. GGTDTC was stable to non‐specific degradation when incubated with a series of prostate cancer and normal cell lines, with selective release of diethyldithiocarbamate only occurring in cells with measurable GGT activity. The antiproliferative efficacy of the prochelator correlated with cellular GGT activity, with 24 h inhibitory concentrations ranging from 800 nm in prostate cancer lines 22Rv1 and LNCaP to over 15 μm in normal prostate PWR‐1E cells. These findings underscore a new strategy to leverage the amplified copper metabolism of prostate cancer by conditional activation of a metal‐binding pharmacophore.
Functionalization in solution of polypropylene with a maleinized hyperbranched polyol polyester: Structural, thermal, rheological, and mechanical properties
Authors: Nova María , Arévalo Yaritza , Murillo Edwin A.
Published: July 2018

The functionalization of polypropylene (PP) with a maleinized hyperbranched polyester polyol (MHBP) was performed in solution to obtain PP‐g‐MHBPs. The degree of functionalization (FD) increased with MHBP and dicumyl peroxide (DCP) contents, but the contact angle followed an opposite behavior. The sample obtained with the proportion of 9.0 wt % MHBP and 2.0 wt % DCP and presented the highest FD value. An FD value of 2.4 wt %, produced a reduction of 19° on the contact angle. It was observed by differential scanning calorimetry (DSC) that the PP‐g‐MHBPs obtained by employing 3.0 wt % of MHBP, exhibited a slight reduction of the melting temperature (Tm) with the increase in the amounts of FD and DCP. Some FD values obtained in this study are higher than those obtained both commercial and noncommercial grades of PP functionalized with maleic anhydride. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 46932.
Revealing early villages – Pseudo‐3D ERT geophysical survey at the pre‐pottery Neolithic site of Kharaysin, Jordan
Authors: Moník Martin , Lenďáková Zuzana , Ibáñez Juan José , Muñiz Juan , Borell Ferrán , Iriarte Eneko , Teira Luis , Kuda František
Published: July 2018

Electric resistivity tomography (ERT) prospection conducted at the Pre‐Pottery Neolithic site at Kharaysin, Jordan, building on previous surface prospection and excavation, found a number of new sub‐surface anomalies. Subsequent excavations determined that the anomalies corresponded with the stone walls of habitation structures and possibly terrace walls. These features covered large areas of the site slope, inclusive of clustered settlement structures and frequent building superpositions indicative of multi‐phase occupation. Despite the generally arid conditions, the moist soil matrix allowed for the effective use of ERT. This article presents the integrated data of the archaeological excavation and the geophysical survey. As a test case it proves the utility of ERT in the identification of Pre‐Pottery Neolithic A (PPNA) and Pre‐Pottery Neolithic B (PPNB) sub‐surface anthropogenic features.
Aggregation‐Induced Emission with Long‐Lived Room‐Temperature Phosphorescence from Methylene‐Linked Organic Donor–Acceptor Structures
Authors: Chen Biao , Zhang Xuepeng , Wang Yucai , Miao Hui , Zhang Guoqing
Published: July 2018

Aggregation‐caused quenching (ACQ), where excited‐state and/or ground‐state electronic structures are altered to exhibit an increased proclivity for non‐radiative decay for the aggregates, is largely responsible for the lack of fluorescence and phosphorescence in molecular solids in general. Here we show that ACQ could be effectively circumvented by constructing an aromatic system with a methylene‐linker, where the system exhibits typical aggregation‐induced emission (AIE) with long‐lived room‐temperature phosphorescence, since the tetrahedral structure in the solid state may significantly reduce strong intermolecular interactions contributing to ACQ.
Larger Pore Size Hollow Fiber Membranes as a Solution to the Product Retention Issue in Filtration‐Based Perfusion Bioreactors
Authors: Wang Samantha B. , Godfrey Scott , Radoniqi Flaka , Lin Henry , Coffman Jon
Published: July 2018

Tangential flow filtration (TFF) and alternating tangential flow (ATF) filtration technologies using hollow fiber membranes are commonly utilized in perfusion cell culture for the production of monoclonal antibodies; however, product retention remains a known and common problem with these systems. To address this issue, commercially available hollow fibers ranging from several hundred kilo‐Daltons (kDa) to 0.65 μm in nominal pore size are tested and are all demonstrated to undergo moderate to severe product retention. Further investigation revealed accumulation of particles in the same size range (≈20–200 nm) as the pores. Based on the assumption that these particles contribute to product retention and membrane plugging, a hollow fiber with an unconventionally larger pore size is subsequently identified and demonstrated to drastically reduce product retention with no impact to cell clarification. Furthermore, these hollow fibers demonstrate surprisingly high membrane capacities, making them an attractive solution to the problem of product retention in perfusion reactors.
Financial burden among older, long‐term cancer survivors: Results from the LILAC study
Authors: Hastert Theresa A. , Young Gregory S. , Pennell Michael L. , Padamsee Tasleem , Zafar S. Yousuf , DeGraffinreid Cecilia , Naughton Michelle , Simon Michael , Paskett Electra D.
Published: July 2018

Background

Increasing attention is being paid to financial burdens of cancer survivorship, but little is known about the prevalence and predictors of these burdens in older, long‐term survivors.

Methods

We used data from 6012 participants diagnosed with cancer since enrolling in the Women's Health Initiative, and who participated in the Life and Longevity After Cancer (LILAC) ancillary study to estimate prevalence and identify predictors of financial burden. We used logistic regression to identify sociodemographic, socioeconomic, health‐ and cancer‐related factors associated with financial burden and backward selection to build a final multivariable model.

Results

Average age at LILAC participation was 79 and 9.2 years had elapsed since cancer diagnosis. Overall, 6% experienced some form of financial burden, including having an insurance company refuse a claim (2.6%), being denied loans or insurance due to cancer history (2.2%), or experiencing significant indebtedness (1.8%, including facing large debts or bills or declaring bankruptcy). Eight predictors remained associated (P < 0.05) with financial burden in the fully‐adjusted model: younger age, shorter time since diagnosis, African‐American race, household income <$20 000/year, modified Charlson comorbidity score ≥2, receipt of chemotherapy, regional stage at diagnosis, and no private health insurance. Education, cancer site, social support, receipt of radiation, and receipt of hormone therapy were not associated with financial burden. Predictors differed between types of financial burden experienced and age at diagnosis (<65 vs 65+).

Conclusion

Cancer‐related financial burden was rare in this population of older, female long‐term cancer survivors. The identification of several socioeconomic, health‐related and demographic predictors of financial burden may suggest targets of intervention to reduce financial burdens.

Precis

Financial burden was uncommon in older, female, long‐term survivors. Predictors of financial burden included age, race, income, comorbidities, time since diagnosis, stage, insurance, and receipt of chemotherapy.
Extracellular calcium regulates the adhesion and migration of osteoclasts via integrin αvβ3/Rho A/Cytoskeleton signaling
Authors: Xiang Bilu , Liu Yang , Zhao Wei , Zhao Hanchi , Yu Haiyang
Published: July 2018

Integrin αvβ3 is a transmembrane integrin, which can initiate osteoclasts’ attachment on bones, leading to downward signaling pathways and subsequent bone resorption. Different calcium concentrations have been reported to have an influence on the activation of integrin αvβ3. To elucidate the regulatory mechanism of extracellular calcium concentrations on osteoclasts, a controlled micro flow plate (M04S) was utilized in the ONIX flow control system to observe the osteoclasts’ adhesion and migration in different calcium concentration media. Fluorescent staining is conducted to show the distribution of integrin αvβ3 and cytoskeleton reorganization. In addition, western blots were performed to detect the expression of integrin αvβ3 and its downstream signaling pathways related to bone resorption. Also, real‐time reverse‐transcription polymerase chain reaction data of transcription co‐activator (YAP/TAZ) and hydrolytic enzymes (the matrix metalloproteinase 9 and cathepsin K) are evaluated. Our findings suggest that osteoclasts’ migration and adhesion is better promoted at 0.5 mM than 1.2 mM, which can be partly explained by the induced cytoskeleton organization via integrin αvβ3/Rho GTPase. But the activation and nuclear localization of YAP/TAZ, and the secretion of hydrolytic enzymes were upregulated when the calcium concentration is at a higher level (1.2 mM). According to our study, there is a high possibility that the migration and attachment of osteoclasts and subsequent osteoclastic bone resorption are regulated over a specific range of extracellular calcium concentration.
Impella‐assisted chronic total occlusion percutaneous coronary interventions: A multicenter retrospective analysis
Authors: Riley Robert F. , McCabe James M. , Kalra Sanjog , Lazkani Mohamad , Pershad Ashish , Doshi Darshan , Kirtane Ajay J. , Nicholson William , Kearney Katherine , Demartini Tony , Aaron Grantham J. , Moses Jeffrey , Lombardi William , Karmpaliotis Dimitri
Published: July 2018

Introduction

Patients with coronary chronic total occlusions (CTO) often have concurrent higher‐risk anatomy and physiology (significant calcium, left ventricular dysfunction, multivessel disease) that increase their procedural risk. We present a retrospective multicenter case series describing use of the Impella percutaneous ventricular assist device (p‐VAD) during CTO PCI.

Methods

We performed a retrospective analysis of self‐reported data from five large referral centers from 2013 to 2017 and identified patients that underwent elective, hemodynamically supported CTO PCI with the Impella p‐VAD device (2.5 or CP). Preprocedural demographics, procedural invasive hemodynamics and characteristics, and in‐hospital outcomes were reported.

Results

About 57 patients (2% of the overall CTO volume of these centers) were included in this retrospective cohort. The primary indication in the majority (78.9%) of cases was chronic angina; in 21.1% the primary indication was for chronic congestive heart failure because of an ischemic cardiomyopathy. The median LVEF was 20% (15%, 30%) and 63.2% were surgical turndowns. Significant proportions of the group underwent multivessel PCI (91.2%), intervention on an unprotected left main or last remaining conduit vessel (35.1%), and/or atherectomy (17.5%). Technical success was 87.7%. In‐hospital procedural complications included: vascular injury (5.3%), all‐cause death (5.3%), major bleeding (3.5%), stroke (1.8%), and coronary perforation resulting in tamponade (1.8%).

Conclusion

Impella‐assisted CTO PCI can be performed with high technical success rates. However, assiduous attention to appropriate case selection is critical, given the periprocedural complication rates reported in this patient population.
Copper‐Catalyzed Monoorganylation of Trialkyl Borates with Functionalized Organozinc Pivalates
Authors: Fu Ying , Gou Bei‐Lei , Shi Chun‐Zhao , Du Zhengyin , Shen Tong
Published: July 2018

Organozinc pivalates, a recently developed air‐ and moisture‐stable organozinc species, were found for the first time as excellent organometallic species in the monoorganylation of trialkyl borates whereby boronic acids were prepared in high yields. The significant advantage of organozinc pivalates over another previously employed organometallic reagents, e. g., organolithium reagents, Grignard reagents and organozinc halides, is that the generation of multiorganylation byproducts such as borinic acids and trialkylboranes were completely suppressed. Additionally, the in situ generated boronates could be directly arranged into Suzuki‐Miyaura type cross‐coupling reactions to produce biaryls in high yields.
Yttrium‐Catalyzed Synthesis of Bipyridine‐Functionalized AB‐Block Copolymers: Micellar Support for Photocatalytic Active Rhenium‐Complexes
Authors: Adams F. , Pschenitza M. , Rieger B.
Published: July 2018

Herein, ortho‐methylated bipyridines are introduced as initiators in 2‐aminoalkoxy‐bis (phenolate) yttrium complexes. For this C−H bond activation (ONOO)tBuY(CH2TMS)(thf) (1) (TMS=trimethylsilyl) is reacted with the respective bipyridine to obtain complexes (ONOO)tBuY(6‐Me2bpy) (2) and (ONOO)tBuY(6‐Mebpy) (3). Both complexes were tested first in rare‐earth metal‐mediated group‐transfer polymerization of 2‐vinylpridine (2VP). Complex 3 was further tested in block copolymerizations of 2VP and diethyl vinylphosphonate. The obtained initiator‐P2VP‐PDEVP‐block copolymers can selectively react with Re(CO)5Cl at their bipyridine end‐group. The obtained rhenium functionalized block copolymers are able to self‐assemble to unimodal micelles in water, representing a possible carrier for hydrophobic metal containing complexes into cells. Furthermore, the Re‐block copolymers sustain activity in the photocatalytic homogeneous CO2 reduction and their performance exceed the catalytic activity of the analogue polymer‐free system [Re(CO)3(6‐Mebpy)Cl] (4).
Enhancing the Catalytic Performance of a CYP116B Monooxygenase by Transdomain Combination Mutagenesis
Authors: Li Ren‐Jie , Xu Jian‐He , Chen Qi , Zhao Jing , Li Ai‐Tao , Yu Hui‐Lei
Published: July 2018

The front cover artwork for Issue 14/2018 is provided by the Laboratory of Biocatalysis and Synthetic Biotechnology, East China University of Science and Technology (ECUST). As shown in the image, a simple transdomain combination mutation strategy (TDCM) was proposed and employed for engineering a self‐sufficient cytochrome P450 monooxygenase (P450LaMO), with significantly improved turnover frequency and electron coupling efficiency. See the Full Paper itself at https://doi.org/10.1002/cctc.201800054.
Non‐Covalently Pre‐Assembled High‐Performance Near‐Infrared Fluorescent Molecular Probes for Cancer Imaging
Authors: Shaw Scott K. , Liu Wenqi , Gómez Durán César Fernando Azael , Schreiber Cynthia L. , Betancourt Mendiola María de Lourdes , Zhai Canjia , Roland Felicia M. , Padanilam Simon J. , Smith Bradley D.
Published: July 2018

New fluorescent molecular probes, which can selectively target specific cell surface receptors, are needed for microscopy, in vivo imaging, and image guided surgery. The preparation of multivalent probes using standard synthetic chemistry can be a laborious process due to low reaction yields caused by steric effects. In this study, fluorescent molecular probes were prepared by a programmed non‐covalent pre‐assembly process that used a near‐infrared fluorescent squaraine dye to thread a macrocycle bearing a cyclic arginine‐glycine‐aspartate peptide antagonist (cRGDfK) as a cancer targeting unit. Cell microscopy studies using OVCAR‐4 (ovarian cancer) and A549 (lung cancer) cells that express high levels of the integrin αvβ3 or αvβ5 receptors, respectively, revealed a multivalent cell targeting effect. That is, there was comparatively more cell uptake of a pre‐assembled probe equipped with two copies of the cRGDfK antagonist than a pre‐assembled probe with only one appended cRGDfK antagonist. The remarkably high photostability and low phototoxicity of these near‐infrared probes allowed for acquisition of long‐term fluorescence movies showing endosome trafficking in living cells. In vivo near‐infrared fluorescence imaging experiments compared the biodistribution of a targeted and untargeted probe in a xenograft mouse tumor model. The average tumor‐to‐muscle ratio for the pre‐assembled targeted probe was 3.6 which matches the tumor targeting performance reported for analogous cRGDfK‐based probes that were prepared entirely by covalent synthesis. The capability to excite these pre‐assembled near‐infrared fluorescent probes with blue or deep‐red excitation light makes it possible to determine if a target site is located superficially or buried in tissue, a probe performance feature that is likely to be very helpful for eventual applications such as fluorescence guided surgery.
Recent Progress on Nickel‐Based Oxide/(Oxy)Hydroxide Electrocatalysts for the Oxygen Evolution Reaction
Authors: Chen Yaping , Rui Kun , Zhu Jixin , Dou Shi Xue , Sun Wenping
Published: July 2018

Developing clean and sustainable energies as alternatives to fossil fuels is in strong demand within modern society. The oxygen evolution reaction (OER) is the efficiency‐limiting process in plenty of key renewable energy systems, such as electrochemical water splitting and rechargeable metal–air batteries. In this regard, ongoing efforts have been devoted to seeking high‐performance electrocatalysts for enhanced energy conversion efficiency. Apart from traditional precious‐metal‐based catalysts, nickel‐based compounds are the most promising earth‐abundant OER catalysts, attracting ever‐increasing interest due to high activity and stability. In this review, the recent progress on nickel‐based oxide and (oxy)hydroxide composites for water oxidation catalysis in terms of materials design/synthesis and electrochemical performance is summarized. Some underlying mechanisms to profoundly understand the catalytic active sites are also highlighted. In addition, the future research trends and perspectives on the development of Ni‐based OER electrocatalysts are discussed.
Ionic Co‐Crystal Formation as a Path Towards Chiral Resolution in the Solid State
Authors: Shemchuk Oleksii , Tsenkova Boryana K. , Braga Dario , Duarte M. Teresa , André Vânia , Grepioni Fabrizia
Published: July 2018

The preparation and characterization of a whole family of hydrated ionic co‐crystals formed by both enantiopure l‐proline and racemic dl‐proline with LiX (X=Cl, Br, I) are reported. The chiral preference of the lithium cation for homochiral coordination, both in the formation of crystalline conglomerates (with Cl and Br) and racemates (with Cl and I), in which molecules of opposite chirality are confined to distinct crystal layers, is discussed. Dehydration processes for all hydrated crystals have also been investigated.
Designing Explosive Poly(Ionic Liquid)s as Novel Energetic Polymers
Authors: Wang Binshen , Feng Yongan , Qi Xiujuan , Deng Mucong , Tian Junjun , Zhang Qinghua
Published: July 2018

The development of ionic‐liquid‐derived functional materials would be vital for stimulation of the interdisciplinary research in the fields of ionic liquid chemistry and material science. Here, a series of novel poly(ionic liquid)s with explosive capability were designed and prepared by introducing the energetic nitrato group and nitro‐rich anions, such as nitrate, dinitramide, and nitroform into the polymeric chains. The as‐synthesized explosive poly(ionic liquid)s (E‐PILs) were fully characterized, and their physicochemical and detonation properties were investigated. All E‐PILs show higher detonation performances than state‐of‐the‐art energetic polymers including glycidyl azide polymer (GAP) and poly(glycidyl nitrate) [poly(GLYN)]. Some E‐PILs exhibit higher calculated detonation velocities and pressures than 2,4,6‐trinitrotoluene (TNT). These E‐PILs are promising candidates for applications as new high‐performance energetic polymers.
Designing Cross‐Coupling Reactions using Aryl(trialkyl)silanes
Authors: Minami Yasunori , Hiyama Tamejiro
Published: July 2018

Organo(trialkyl)silanes have several advantages, including high stability, low toxicity, good solubility, easy handling, and ready availability compared with heteroatom‐substituted silanes. However, methods for the cross‐coupling of organo(trialkyl)silanes are limited, most probably because of their exceeding robustness. Thus, a practical method for the cross‐coupling of organo(trialkyl)silanes has been a long‐standing challenging research target. This article discusses how aryl(trialkyl)silanes can be used in cross‐coupling reactions. A pioneering example is CuII catalytic conditions with the use of electron‐accepting aryl‐ or heteroaryl(triethyl)silanes and aryl iodides. The reaction forms biaryls or teraryls. This design concept can be extended to Pd/CuII‐catalyzed cross‐coupling polymerization reactions between such silanes and aryl bromides or chlorides and to CuI‐catalyzed alkylation using alkyl halides.
Activation of O−H and C−O Bonds in Water and Methanol by a Vanadium‐Bound Thiyl Radical
Authors: Yan Jyun‐An , Yang Zi‐Kuan , Chen Yu‐Sen , Chang Ya‐Ho , Lyu Chiao‐Ling , Luo Chun‐Gang , Cheng Mu‐Jeng , Hsu Hua‐Fen
Published: July 2018

The reaction of [V(PS3“)]− (1) (PS3”=[P(C6H3‐3‐Me3Si‐2‐S)3]3−) with H2O led to the formation of [VIV(PS3“)(PS2”SH)]− (2) (PS2“SH=[P(C6H3‐3‐Me3Si‐2‐S)2(C6H3‐3‐Me3Si‐2‐SH)]2−), indicating a hydrogen atom transfer from H2O to a bound thiolate in 1. Furthermore, the reaction of 1 with CH3OH gave the generation of complexes 2 and 3, [VIV(PS3”)(PS2“SCH3)]− (PS2”SCH3=[P(C6H3‐3‐Me3Si‐2‐S)2(C6H3‐3‐Me3Si‐2‐SCH3)]2−), implying that C−O and O−H bonds are cleaved by 1. Quantum mechanical calculations were performed to provide the mechanistic understanding for the reactivity of 1 with water. A key transition state with a lower kinetic barrier is identified. It involves an O−H bond cleavage by a dissociated thiyl radical with an interaction between an OH group and a neighboring bound sulfur donor. To our knowledge, the reactivity of 1 represents a new mode for water activation conducted through cooperation between a metal‐stabilized thiyl radical and a neighboring thiolato donor.
Investigation of growth kinetics of Debaryomyces hansenii (LAF‐3 10 U) in petroleum refinery desalter effluent
Authors: Azimian Leila , Bassi Amarjeet , Mercer Sean M.
Published: July 2018

Desalter effluent is a difficult to treat wastewater stream emerging from petroleum refining operations. In this study, an osmotolerant and halotolerant yeast, Debaryomyces hansenii, was investigated for the first time for its use in removing phenol from simulated and actual desalter effluent. D. hansenii was able to degrade phenols at substrate COD concentrations ranging from 300–1200 mg L−1, whereas the substrate inhibition was noted as COD increased from 2000–4000 mg L−1. Three kinetic models (Andrews, Aiba, and Edward) were applied as unstructured mathematical models to simulate substrate inhibition kinetics with respect to phenol COD. Among all models, the Edward model best simulated the yeast growth on phenol. Using the Edward model, the model parameters were μmax 0.21 h−1, KS 633.95 mg · L−1, and KI 1263.61 mg · L−1, respectively. The results in this study confirmed that D. hansenii has a high tolerance toward phenols and other organic compounds and salt found in desalter effluent. This yeast is therefore suggested to serve as an appropriate system from biological treatment of phenolic wastes in difficult to treat effluents such as desalter effluent.
Nickel‐Catalyzed Direct Coupling of Allylic Alcohols with Organoboron Reagents
Authors: Wang Gaonan , Gan Yi , Liu Yuanhong
Published: July 2018

The direct coupling of allylic alcohols with arylboronic acids or their derivatives catalyzed by Ni(cod)2 in the presence of a catalytic amount of base has been developed. A wide variety of allylic substrates or arylboronic acids turned out to be applicable to this catalytic system. The present method does not require the use of ligands for stabilizing the nickel catalyst in most cases or additional activators for activation of allylic alcohols.
QRS voltage is a predictor of in‐hospital mortality of acutely ill medical patients
Authors: Kellett John , Opio Martin Otyek ,   Kitovu Hospital Study Group
Published: July 2018

Background

Low QRS voltage has been shown to be associated with increased mortality in the general population and in a small pilot study the combined QRS voltage of ECG leads I and II was found to be associated with in‐hospital mortality.

Hypothesis

Confirm that low QRS voltage predicts the in‐hospital mortality of acutely ill patients, and compare QRS voltage with other predictors of mortality that can be easily, quickly and cheaply obtained at the bedside.

Methods

Prospective observational study of vital signs, QRS voltage and simple tools used to assess mental, functional and nutritional status at the bedside in unselected acutely ill patients admitted to a resource‐poor hospital in sub‐Saharan Africa.

Results

Out of 1486 patients, 77 died (5.2%) in hospital. A combined lead I + II voltage <1.8 mV was present in 789 (53.1%) of patients, and significantly associated with in‐hospital mortality (odds ratio 3.6, 95% CI 2.0‐6.5, χ2 21.2, P < 0.00001). On logistic regression impaired mobility, the National Early Warning Score, male gender and lead I + II voltage were the only independent predictors of mortality. None of the 445 patients who were mobile on admission with a lead I + II voltage ≥ 1.8 mV died in hospital.

Conclusions

Low QRS voltage, male gender, NEWS, and impaired mobility were independent predictors of in‐hospital mortality in the study population. These four variables, which are easily obtained at the bedside, could potentially provide a rapid, easy, and cheap risk stratification system.
Combined Ligand‐ and Receptor‐Based Virtual Screening Methodology to Identify Structurally Diverse Protein Tyrosine Phosphatase 1B Inhibitors
Authors: Gimeno Aleix , Ardid‐Ruiz Andrea , Ojeda‐Montes María José , Tomás‐Hernández Sarah , Cereto‐Massagué Adrià , Beltrán‐Debón Raúl , Mulero Miquel , Valls Cristina , Aragonès Gerard , Suárez Manuel , Pujadas Gerard , Garcia‐Vallvé Santiago
Published: July 2018

Protein tyrosine phosphatase 1B (PTP1B) is a potential drug target for diabetes and obesity. However, the design of PTP1B inhibitors that combine potency and bioavailability is a great challenge, and new leads are needed to circumvent this problem. Virtual screening (VS) workflows can be used to find new PTP1B inhibitors with little chemical similarity to existing inhibitors. Unfortunately, previous VS workflows for the identification of PTP1B inhibitors have several limitations, such as a small number of experimentally tested compounds and the low bioactivity of those compounds. We developed a VS workflow capable of identifying 15 structurally diverse PTP1B inhibitors from 20 compounds, the bioactivity of which was tested in vitro. Moreover, we identified two PTP1B inhibitors with the highest bioactivity reported by any VS campaign (i.e., IC50 values of 1.4 and 2.1 μm), which could be used as new lead compounds.
Use of seasonal forecasting to manage weather risk in ecological restoration
Authors: Hagger Valerie , Dwyer John , Shoo Luke , Wilson Kerrie
Published: July 2018

Ecological restoration has widely variable outcomes from successes to partial or complete failures, and there are diverse perspectives on the factors that influence the likelihood of success. However, not much is known about how these factors are perceived, and whether people's perceptions match realities. We surveyed 307 people involved in the restoration of native vegetation across Australia to identify their perceptions on the factors influencing the success of restoration projects. We found that weather (particularly drought and flooding) has realized impacts on the success of restoration projects, but is not perceived to be an important risk when planning new projects. This highlights the need for better recognition and management of weather risk in restoration and a potential role of seasonal forecasting. We used restoration case studies across Australia to assess the ability of seasonal forecasts provided by the Predictive Ocean Atmosphere Model for Australia, version M24 (POAMA‐2) to detect unfavorable weather with sufficient skill and lead time to be useful for restoration projects. We found that rainfall and temperature variables in POAMA‐2 predicted 88% of the weather issues encountered in restoration case studies apart from strong winds and cyclones. Of those restoration case studies with predictable weather issues, POAMA‐2 had the forecast skill to predict the dominant or first‐encountered issue in 67% of cases. We explored the challenges associated with uptake of forecast products through consultation with restoration practitioners and developed a prototype forecast product using a local case study. Integrating seasonal forecasting into decision making through (1) identifying risk management strategies during restoration planning, (2) accessing the forecast a month prior to revegetation activities, and (3) adapting decisions if extreme weather is forecasted, is expected to improve the establishment success of restoration.
Trophic transfer from aquatic to terrestrial ecosystems: a test of the biogeochemical niche hypothesis
Authors: Bartrons Mireia , Sardans Jordi , Hoekman David , Peñuelas Josep
Published: July 2018

Matter and energy flow across ecosystem boundaries. Transfers from terrestrial to aquatic ecosystems are frequent and have been widely studied, but the flow of matter from aquatic to terrestrial ecosystems is less known. Large numbers of midges emerge from some lakes in northern Iceland and fly to land. These lakes differ in their levels of eutrophication due to different intensities of geothermal warming and nutrient inputs. In the context of this material transfer from an aquatic to a terrestrial ecosystem, we investigated the relationships between the deposition of midges and the elemental composition and stoichiometry of organisms in low‐productivity terrestrial ecosystems. We analyzed several terrestrial food webs in northeastern Iceland with similar food web compositions of terrestrial arthropods but different inputs of midges and analyzed the stoichiometric composition of the different trophic groups. Elemental composition differed among trophic groups and taxa much more than within each trophic group or taxa across the midge deposition gradient. Specifically, the change in N concentration was significant in plants (up to 70% increase in the site with maximum input) but not in predators, which had a more homeostatic elemental composition. These results thus show (1) a significant movement of matter and nutrients from an aquatic to a terrestrial habitat via the emergence of aquatic insects and the deposition of insect carcasses, (2) a larger impact on the elemental composition of plants than arthropods, and (3) support for the biogeochemical niche hypothesis, which predicts that different species should have a specific elemental composition, stoichiometry, and allocation as a consequence of their particular metabolism, physiology, and structure.