bluuebunny/crossref_metadata_2025 huggingface dataset:
Surface‐modified halloysite nanotubes reinforced poly(lactic acid) for use in biodegradable coronary stents
Authors: Chen Yuanyuan , Murphy Alan , Scholz Dimitri , Geever Luke M. , Lyons John G. , Devine Declan M.
Published: April 2018

Poly(lactic acid) (PLA) was reinforced halloysite nanotubes (HNTs) in this study. To improve dispersion and interfacial adhesion of HNTs within the PLA matrix, HNTs were surface modified with 3‐aminopropyltriethoxysilane (ASP) prior to compounding with PLA. PLA/ASP‐HNTs nanocomposites were characterized by differential scanning calorimetry (DSC), Fourier transfer infrared spectroscopy (FTIR), surface wettability, thermogravimetric analysis, transmission electron microscopy (TEM), and tensile testing. The hemocompatibility and cytocompatibility of PLA and PLA composites were investigated and thein vitrodegradation process of PLA/ASP‐HNTs composites was investigated for a period of 6 months by gel permeation chromatography, FTIR, weight loss measurement, DSC, and tensile testing. PLA and all PLA composites were blood compatibile and non‐cytotoxic. TEM analysis revealed that HNTs agglomeration in PLA matrix was reduced by surface treatment with ASP. ASP‐HNTs had better reinforcing effect than unmodified HNTs evidenced by tensile testing. ASP‐HNTs appeared to increase the hydrolytic degradation process as measured by weight measurement. PLA/ASP‐HNTs composites displayed 12.1% weight loss and 30.6% average molecular weight reduction while retaining 74% of Young's modulus by the 24th week of degradation. Based on this data, the reinforcement of PLA using ASP‐HNTs may prove beneficial for applications such as biodegradable stents. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci.2018,135, 46521.
High efficiency toughness of aromatic sulfonamide in polyamide 6
Authors: Jia Zhenyu , Cai Ziqing , Chen Jianwen , Zhang Li , Yang Fan , Que Xianlang , Bao Haifeng
Published: April 2018

In order to overcome the brittle fracture characteristics of polyamides, the study on high efficiency toughening of polyamides is always a hot topic. In this article, n‐ethyl‐p‐toluene sulfonamide (N‐PTSA) was used as the toughening agent in polyamide 6 (PA6) matrix. The PA6/N‐PTSA composites were prepared by melt compounding method. The PA6 composites were analyzed systematically from aspects of mechanical properties, thermal properties, crystal structures, and hydrogen bonds. There existed an obvious toughening effect in PA6 composite with the addition of 7 wt % of N‐PTSA. Meanwhile, the tensile strength of the composite was not reduced. The addition of N‐PTSA induced the formation of α‐form crystals, higher crystallinities and lower density of hydrogen bonds in the composites, which was beneficial to improvement of the mechanical properties. Based on the above results, the molecular structure model of toughening mechanism of N‐PTSA in PA6 was established. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46527.
Mussel‐inspired magnetic adsorbent: Adsorption/reduction treatment for the toxic Cr(VI) from simulated wastewater
Authors: Dong Kaijie , Liu Qinze , Wei Gang , Hu Tao , Yao Jinshui , Zhang Xian , Gao Tingting
Published: April 2018

A novel magnetic adsorbent, poly(catechol‐1,4‐butanediamine)‐coated Fe3O4 composite (Fe3O4@PCBA), was successfully fabricated via an easy and gentle method according to the mussel‐inspired adhesion property of polydopamine. Effects of many factors on the adsorption performance of Fe3O4@PCBA for Cr(VI) were investigated, including temperature, pH value, contacting time, adsorbent dosage, and initial Cr(VI) concentration. The thermodynamics, adsorption isotherm, kinetics, and intraparticle diffusion of adsorption were also studied systematically. Results indicated that the removal rate of Cr(VI) was approximately close to 100% when the initial concentration was less than 120 mg/L, and the maximum uptake capacity of Fe3O4@PCBA for Cr(VI) was 280.11 mg/g complied with Langmuir isotherm model. Accordingly, the nocuous Cr(VI) could be partially reduced to Cr(III) during the adsorption period. Hopefully, this strategy could be extended to prepare series of magnetic Fe3O4@catechol–amine adsorbents with different amino and phenolic hydroxyl groups for Cr(VI) removal. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46530.
The Price of Ill‐programmed Self‐defense – We Must Face What We Do,
Authors: Parens Henri
Published: April 2018

Throughout history, large‐groups in conflict have in the name of self‐defense carried out preemptive attacks against those who threatened their land and its people. While such attacks have often brought accolades and praise from the perpetrating group, from the mid‐twentieth century on, especially following on the 1948 United Nations (UN) Universal Declaration of Human Rights, there has been a sharper‐than‐before ideological shift away from “Might is Right” toward responsibility for “Crimes against Humanity”. While the perpetrating group's glories have brought the generations that follow much pride, increasingly the group's breach of Geneva‐type Conventions and the UN Universal Declaration of Human Rights have brought condemnation which has wrought guilt and shame to the perpetrator's children and their children. There are renowned examples in history of such collective guilt and shame that have become part of the perpetrating large‐group's identity and psyche, such as (1) the United States' importing slavery which to this day brings not only guilt and shame to many of us, but also continuous events of turmoil to our society that so ignobly treated African Americans; and, (2) several generations of Germans today continue to experience profound shame and guilt for what their Nazi Third Reich forbearers did to about 11 million “undesirables”. While certainly not comparable to these abominable examples, should not Israel be consciously aware of the consequences of perpetrating on the Palestinians unduly provocative and destructive self‐defense strategies that may in consequence be costly to the Jewish people's collective psyche and induce much guilt and shame in generations of Jews that will follow us?
The Amniote Oculomotor Complex
Authors: Company Verónica , Moreno‐Bravo Juan Antonio , Perez‐Balaguer Ariadna , Puelles Eduardo
Published: April 2018

The oculomotor (OM) complex is a combination of somatic and parasympatethic neurons. The correct development and wiring of this cranial pair is essential to perform basic functions: eyeball and eyelid movements, pupillary constriction, and lens accommodation. The improper formation or function of this nucleus leads pathologies such as strabismus. We describe the OM organization and function in different vertebrate brains, including chick, mouse, and human. The morphological localization is detailed, as well as the spatial relation with the trochlear nucleus in order to adjust some misleading anatomical topographic descriptions. We detailed the signaling processes needed for the specification of the OM neurons. The transcriptional programs driven the specification and differentiation of these neurons are partially determined. We summarized recent genetic studies that have led to the identification of guidance mechanisms involved in the migration, axon pathfinding, and targeting of the OM neurons. Finally, we overviewed the pathology associated to genetic malformations in the OM development and related clinical alterations. Anat Rec, 302:446–451, 2019. © 2018 Wiley Periodicals, Inc.
A Constructive Globally Convergent Adaptive Speed Observer For Port‐Hamiltonian Mechanical Systems with Non‐Holonomic Constraints
Authors: Touati Brahim Ammar , Kidouche Madjid
Published: April 2018

This paper presents an adaptive speed observer for general port‐Hamiltonian mechanical systems with non‐holonomic constraints in the presence of unknown friction forces and constant disturbances. Unlike the observers recently reported in the literature, which have been designed either under the assumptions of no friction and the absence of disturbances or for a specific class of mechanical systems with the requirement of an explicit solution of certain Partial Differential Equations (PDEs) that cannot be derived a priori, this observer proposes a design that obviates the solution of PDEs and ensures global convergence for general mechanical systems with k‐non‐holonomic constraints. The observer is totally constructive and given by explicit expressions. The simulation results testify to the effectiveness and the robust features of the developed observer.
Konstruktiver Wasserbau in der Normung
Authors: Kunz Claus
Published: April 2018

Normen des konstruktiven Wasserbaus werden im DIN‐Normenausschuss Wasserwesen (NAW), hier Fachbereich Wasserbau (NA 119‐02 FB), bearbeitet. Der Fachbereich wird im Zusammenhang mit dem Normenausschuss Wasserwesen und mit seinem Portfolio vorgestellt. In Überarbeitung befindliche Normen werden kurz dargestellt. In einem Ausblick werden weitere Normen benannt, die zeitnah überarbeitet werden sollen, aber auch mögliche künftige Normungsaktivitäten. Der Fachbereich wird hierzu jeweils in den einschlägigen Fachzeitschriften Aufrufe zur Mitarbeit lancieren.
Microalgae processing for jet fuel production
Authors: Bwapwa Joseph K. , Anandraj Akash , Trois Cristina
Published: April 2018

This study focuses on the laboratory production of jet fuel from microalgae. In contrast with many studies that use partial nutrient starvation to boost lipid content of the species, physiological modification was undertaken under complete nutrient starvation for 3 days to increase lipid content beyond 80%. This was followed by biomass harvesting, which was necessary for downstream processes. Large amounts of biomass were achieved between day 8 and day 10 during the cultivation period, with temperatures ranging between 15 and 35 °C under constant luminance of 1000 lux and daily supply of CO2 for 15 days. It was found that Nannochloropsis sp. grew effectively between 15 °C and 25 °C with more biomass produced in the same temperature range. Conversion processes involved steps such as oil extraction, thermal cracking without catalyst at 300 °C and fractionation between 70 °C and 250 °C. The pyrolysis of bio‐oil was also undertaken as a fast cracking process for the temperature ranging between 350 °C and 450 °C within 12 s. Some parameters such as flash point, net heat of combustion, sulfur, and viscosity complied with ASTM standards. Jet fuel from microalgae therefore shows potential despite many challenges related to cost effectiveness and sustainability. In order to obtain a bio‐jet fuel that is completely compliant with ASTM standards, upgrading, reforming processes, and the use of additives will be needed more, especially for pilot and large‐scale production once fuel sustainability is achieved. © 2018 Society of Chemical Industry and John Wiley & Sons, Ltd
A Stable Artificial Multienzymatic Complex Using a Heterotrimeric Protein From Metallosphaera sedula
Authors: Iwata Fumiya , Hirakawa Hidehiko , Nagamune Teruyuki
Published: April 2018

Bacterial cytochrome P450 monooxygenases (P450s) are promising biocatalysts for chemical syntheses because they catalyze a variety of oxidations on non‐activated hydrocarbons using O2. However, the requirement of two auxiliary proteins, an electron transfer protein and a reductase, for the catalysis is a major bottleneck for in vitro applications of these monooxygenases. The authors previous study showed that artificial assembly of a bacterial P450 with its auxiliary proteins using a heterotrimeric proliferating cell nuclear antigen (PCNA) from Sulfolobus solfataricus yields a self‐sufficient P450, but partial dissociation of P450 from the complex at catalytic concentrations reduces the apparent specific activity of this self‐sufficient P450. In this study, a Metallosphaera sedula PCNA is used, which is currently the most stable heterotrimeric PCNA, to assemble a bacterial P450 with its auxiliary proteins at submicromolar protein concentrations. The apparent specific monooxygenase activity of the M. sedula PCNA‐assembled P450 with auxiliary proteins is saturated at protein concentrations of 40 nM, and is 2.1‐fold higher than that of the S. solfataricus PCNA‐assembled P450. Therefore, M. sedula PCNA represents a versatile tool to facilitate multiple enzymatic reactions, including the P450 monooxygenase system.
Anhydrous polymer‐based coating with sustainable controlled release functionality for facile, efficacious impregnation, and delivery of antimicrobial peptides
Authors: Lim Kaiyang , Saravanan Rathi , Chong Kelvin K. L. , Goh Sharon H. M. , Chua Ray R. Y. , Tambyah Paul A. , Chang Matthew W. , Kline Kimberly A. , Leong Susanna S. J.
Published: April 2018

Anhydrous polymers are actively explored as alternative materials to overcome limitations of conventional hydrogel‐based antibacterial coating. However, the requirement for strong organic solvent in polymerization reactions often necessitates extra protection steps for encapsulation of target biomolecules, lowering encapsulation efficiency, and increasing process complexity. This study reports a novel coating strategy that allows direct solvation and encapsulation of antimicrobial peptides (HHC36) into anhydrous polycaprolactone (PCL) polymer‐based dual layer coating. A thin 1‐palmitoyl‐2‐oleoyl‐sn‐glycero‐3‐phosphocholine (POPC) film is layered onto the peptide‐impregnated PCL as a diffusion barrier, to modulate and enhance release kinetics. The impregnated peptides are eventually released in a controlled fashion. The use of 2,2,2‐trifluoroethanol (TFE), as polymerization and solvation medium, induces the impregnated peptides to adopt highly stable turned conformation, conserving peptide integrity, and functionality during both encapsulation and subsequent release processes. The dual layer coating showed sustained antibacterial functionality, lasting for 14 days. In vivo assessment using an experimental mouse wounding model demonstrated good biocompatibility and significant antimicrobial efficacy of the coating under physiological conditions. The coating was translated onto silicone urinary catheters and showed promising antibacterial efficacy, even outperforming commercial silver‐based Dover cather. This anhydrous polymer‐based platform holds immense potential as an effective antibacterial coating to prevent clinical device‐associated infections. The simplicity of the coating process enhances its industrial viability.
Two-year results of the randomized clinical trial DILALA comparing laparoscopic lavage with resection as treatment for perforated diverticulitis
Authors: Kohl A , Rosenberg J , Bock D , Bisgaard T , Skullman S , Thornell A , Gehrman J , Angenete E , Haglind E
Published: April 2018

Background

Traditionally, perforated diverticulitis with purulent peritonitis was treated with resection and colostomy (Hartmann's procedure), with inherent complications and risk of a permanent stoma. The DILALA (DIverticulitis – LAparoscopic LAvage versus resection (Hartmann's procedure) for acute diverticulitis with peritonitis) and other randomized trials found laparoscopic lavage to be a feasible and safe alternative. The medium-term follow-up results of DILALA are reported here.

Methods

Patients were randomized during surgery after being diagnosed with Hinchey grade III perforated diverticulitis at diagnostic laparoscopy. The primary outcome was the proportion of patients with one or more secondary operations from 0 to 24 months after the index procedure in the laparoscopic lavage versus Hartmann's procedure groups. The trial was registered as ISRCTN82208287.

Results

Forty-three patients were randomized to laparoscopic lavage and 40 to Hartmann's procedure. Patients in the lavage group had a 45 per cent reduced risk of undergoing one or more operations within 24 months (relative risk 0·55, 95 per cent c.i. 0·36 to 0·84; P = 0·012) and had fewer operations (ratio 0·51, 95 per cent c.i. 0·31 to 0·87; P = 0·024) compared with those in the Hartmann's group. No difference was found in mean number of readmissions (1·37 versus 1·50; P = 0·221) or mortality between patients randomized to laparoscopic lavage or Hartmann's procedure. Three patients in the lavage group and nine in the Hartmann's group had a colostomy at 24 months.

Conclusion

Laparoscopic lavage is a better option for perforated diverticulitis with purulent peritonitis than open resection and colostomy.
Potential case of gynecomastia in mummified remains of an early modern period northern finnish vicar
Authors: Väre Tiina , Galassi Francesco M. , Niinimäki Jaakko , Junno Juho‐Antti
Published: April 2018

We report possibly the oldest evidence of gynecomastia in mummified human remains. Computed tomography was performed on the mummified remains of an early 17th century Northern Finnish vicar. The examination of the scans revealed large bilateral subareolar irregular masses resembling female mammary glands. The nearly septuagenarian vicar appears to have had gynecomastia, as it is a common condition in elderly men, and is sometimes associated with obesity. Gynecomastia is the most likely explanation for these findings. Clin. Anat. 31:641–644, 2018. © 2018 Wiley Periodicals, Inc.
The importance of nutritional interventions for incarcerated youth
Authors: Magaziner Sarah
Published: April 2018

The consumption of adequate nutrition in adolescence can have long‐term positive effects on physical and emotional development, contributing to the prevention of several chronic diseases, including obesity, coronary heart disease, stroke, and Type 2 diabetes. While many of these diseases are not detected until adulthood, childhood obesity has emerged as a significant public health issue. The prevalence of obesity has doubled among American youth in the past three decades, with the most recent data confirming that one in three children in the United States are clinically overweight or obese.
Keep your eye on…
Authors: Knopf Alison
Published: April 2018

A treasure trove of data on the adolescent brain

The value of school‐based services
DMDD should be diagnosable in preschool‐age children: Researchers
Authors: Knopf Alison
Published: April 2018

Frustration is a normal response to blocked attainment of a goal, but irritability is a tendency to respond to frustration with increased anger. Mild temper tantrums — normal manifestations of anger in early childhood — are different from pervasive and dysregulated temper tantrums. But the connection between such early behavior and later disorders has been difficult to make. And while irritability is representing in a number of DSM‐5 diagnoses, the manual has no specific developmental definition of irritability.
Student Success in Developmental Math Education: Connecting the Content at Ivy Tech Community College
Authors: Royer Dan W. , Baker Russell D.
Published: April 2018

This chapter considers difficulties with traditionally organized developmental math course sequences from the literature and practice. We then report initial student success findings following the system‐wide implementation of a corequisite model in developmental math.
The Oregon Model for Improving Student Completion Through Developmental Education Reform
Authors: Brand Elizabeth Cox
Published: April 2018

This chapter outlines the beginning of this important work in Oregon; describes how we are able to make such dramatic change across the state without being a system or having a mandate, progress to date, and future directions.
Accelerating Remedial Education in Louisiana
Authors: Campbell Emily , Cintron Rene
Published: April 2018

This chapter describes the implementation and outcomes of a multiyear pilot study on the use of the corequisite model in math and English remediation. Practical recommendations are presented after an analysis of student outcomes and institutional practices.
Improving Developmental Education Reform in Florida
Authors: Waschull Stefanie B.
Published: April 2018

This chapter explores early impacts from the Florida College system's bold experiment in making placement testing and developmental education optional for most students.
Persistent Pedagogical Challenges in Developmental Education Reform
Authors: Cox Rebecca D.
Published: April 2018

This chapter presents pedagogical challenges to reform in developmental education and observations of best practices gleaned from successful mathematics developmental education classrooms.
Echocardiography in pulmonary hypertension: current evidence and future perspectives
Authors: Grapsa J. , Tzemos N.
Published: April 2018

Pulmonary hypertension is a debilitating disease with limited treatment options and prognosis. A significant part of right heart failure management is the accurate imaging of right heart chambers with the means of conventional echocardiography as well as advanced imaging. The purpose of this review was to explain the anatomy and physiology of the right heart chambers and subsequently to demonstrate all latest available echocardiographic indices specific for right heart. We also discuss three‐dimensional echocardiography and speckle tracking as advanced imaging modalities for right heart assessment.
Long‐Lasting Non‐hydrogenated Dark Titanium Dioxide: Medium Vacuum Anneal for Enhanced Visible Activity of Modified Multiphase Photocatalysts
Authors: Ozer Lütfiye Y. , Apostoleris Harry , Ravaux Florent , Shylin Sergii I. , Mamedov Fikret , Lindblad Andreas , Johansson Fredrik O. L. , Chiesa Matteo , Sá Jacinto , Palmisano Giovanni
Published: April 2018

Multiphase TiO2 was stably modified by vacuum treatment for a dramatic improvement in visible‐light absorption and photocatalytic reactivity. The samples were made of rutile‐brookite, bare or N doped, and were grown on reduced graphene oxide. The stable introduction of Ti3+ species and oxygen vacancies resulting in mitigated electron–hole recombination was identified as the main responsible factor, along with a change in surface charges.
Solid‐State and Solution‐Mediated Polymorphic Transformation of Rifampicin
Authors: Jing Dingding , Gu Yuan , Xia Huiming
Published: April 2018

Rifampicin, a semisynthetic broad‐spectrum antibiotic with antibacterial activity for a variety of pathogenic microorganisms, has three crystal forms, namely, I, II, and SV. Forms I and II are bioavailable. Solid‐state polymorphic transformation (SST) from Form II to I and solution‐mediated polymorphic transformation (SMT) from Form I to II were investigated by offline X‐ray diffraction (PXRD) and Fourier transform infrared spectroscopy (FTIR), respectively. Solubility and supersolubility of rifampicin Forms I and II in different solvents were obtained using the static method and turbidity meter method separately. The thermodynamic study of rifampicin proved that crystal Form I was more stable than Form II. These studies were necessary to optimize the crystallization process and crystal form controlling. The bulk density which influences significantly the drug loading capacity was clearly developed.
Slow Magnetic Relaxation in a Palladium–Gadolinium Complex Induced by Electron Density Donation from the Palladium Ion
Authors: Izuogu David C. , Yoshida Takefumi , Zhang Haitao , Cosquer Goulven , Katoh Keiichi , Ogata Shuhei , Hasegawa Miki , Nojiri Hiroyuki , Damjanović Marko , Wernsdorfer Wolfgang , Uruga Tomoya , Ina Toshiaki , Breedlove Brian K. , Yamashita Masahiro
Published: April 2018

Incorporating palladium in the first coordination sphere of acetato‐bridged lanthanoid complexes, [Pd2Ln2(H2O)2(AcO)10]⋅2 AcOH (Ln=Gd (1), Y (2), Gd0.4Y1.6 (3), Eu (4)), led to significant bonding interactions between the palladium and the lanthanoid ions, which were demonstrated by experimental and theoretical methods. We found that electron density was donated from the d8 Pd2+ ion to Gd3+ ion in 1 and 3, leading to the observed slow magnetic relaxation by using local orbital locator (LOL) and X‐ray absorption near‐edge structure (XANES) analysis. Field‐induced dual slow magnetic relaxation was observed for 1 up to 20 K. Complex 3 and frozen aqueous and acetonitrile solutions of 1 showed only one relaxation peak, which confirms the role of intermolecular dipolar interactions in slowing the magnetic relaxation of 1. The slow magnetic relaxation occurred through a combination of Orbach and Direct processes with the highest pre‐exponential factor (τo=0.06 s) reported so far for a gadolinium complex exhibiting slow magnetic relaxation. The results revealed that transition metal–lanthanoid (TM–Ln) axial interactions indeed could lead to new physical properties by affecting both the electronic and magnetic states of the compounds.
Metal Cluster Electrides: A New Type of Molecular Electride with Delocalised Polyattractor Character
Authors: El Bakouri Ouissam , Postils Verònica , Garcia‐Borràs Marc , Duran Miquel , Luis Josep M. , Calvello Simone , Soncini Alessandro , Matito Eduard , Feixas Ferran , Solà Miquel
Published: April 2018

Electrides are ionic substances containing isolated electrons. These confined electrons are topologically characterised by a quasi‐atom, that is, a non‐nuclear attractor (NNA) of the electron density. The electronic structure of the octahedral4A1gLi6+and5A1gBe6species shows that these species have a large number of NNAs. These NNAs have highly delocalised electron densities and, as a result, the chemical bonding pattern of these systems is reminiscent of that in solid metals, in which metal cations are surrounded by a “sea” of delocalised valence electrons. We propose the term metal cluster electrides to refer to this new class of compounds. In this study, we establish a computational protocol to identify, characterize, and design metal cluster electrides and we elucidate the intricate bonding patterns of this particular type of species.
Design and Synthesis of Iminosydnones for Fast Click and Release Reactions with Cycloalkynes
Authors: Riomet Margaux , Decuypere Elodie , Porte Karine , Bernard Sabrina , Plougastel Lucie , Kolodych Sergii , Audisio Davide , Taran Frédéric
Published: April 2018

Emerging applications in the field of chemical biology are currently limited by the lack of bioorthogonal reactions allowing both removal and linkage of chemical entities on complex biomolecules. We recently discovered a novel reaction between iminosydnones and strained alkynes leading to two products resulting from ligation and fragmentation of iminosydnones under physiological conditions. We now report the synthesis of a panel of substituted iminosydnones and the structure reactivity relationship between these compounds and strained alkyne partners. This study identified the most relevant substituents, which allow to increase the rate of the transformation and to develop a bifunctional cleavable linker with improved kinetics.
Probing Optical Anisotropy and Polymorph‐Dependent Photoluminescence in [Ln2] Complexes by Hyperspectral Imaging on Single Crystals
Authors: Errulat Dylan , Gabidullin Bulat , Murugesu Muralee , Hemmer Eva
Published: April 2018

Two homodinuclear and one heterodinuclear lanthanide (Ln)‐based complexes of the general formula [Ln2(bpm)(tfaa)6] (Ln=Eu (1), Tb (2), Eu−Tb (3), bpm=2,2′‐bipyrimidine, tfaa−=1,1,1‐trifluoroacetylacetonate) were synthesized and characterized by single‐crystal photoluminescence spectroscopy and hyperspectral imaging. Complexes 1 and 2 crystallize in two polymorphic structures, while three polymorphs were isolated for 3, namely having needle‐, plate‐, and block‐like morphologies. Single‐crystal photoluminescence spectroscopy and imaging on Eu3+‐containing 1 and 3 revealed polymorph‐dependent J‐splitting of the hypersensitive 5D0→7F2 Eu3+ transition as well as electric‐to‐magnetic dipole emission intensity ratios. According to these observations, the lowest symmetry chemical environment was attributed to the Eu3+ ions present in the needle‐like polymorph, also in agreement with single‐crystal X‐ray diffraction analysis. More importantly, hyperspectral imaging on all three single‐crystal polymorphs of 3 exhibits optical anisotropy with photoluminescence enhancement at specific crystallographic faces. This behavior was ascribed to the distinct molecular packing of the Ln−Ln dimers in each polymorphic crystal as well as to face‐specific local symmetry of the Eu3+ centers. Overall, opto‐structural relationships of three Ln−Ln dimers and their single‐crystal polymorphs were established as a particularly promising avenue for control of photoluminescence by chemical crystal engineering.
Reversible Ligand‐Centered Reduction in Low‐Coordinate Iron Formazanate Complexes
Authors: Broere Daniël L. J. , Mercado Brandon Q. , Lukens James T. , Vilbert Avery C. , Banerjee Gourab , Lant Hannah M. C. , Lee Shin Hee , Bill Eckhard , Sproules Stephen , Lancaster Kyle M. , Holland Patrick L.
Published: April 2018

Coordination of redox‐active ligands to metals is a compelling strategy for making reduced complexes more accessible. In this work, we explore the use of redox‐active formazanate ligands in low‐coordinate iron chemistry. Reduction of an iron(II) precursor occurs at milder potentials than analogous non‐redox‐active β‐diketiminate complexes, and the reduced three‐coordinate formazanate‐iron compound is characterized in detail. Structural, spectroscopic, and computational analysis show that the formazanate ligand undergoes reversible ligand‐centered reduction to form a formazanate radical dianion in the reduced species. The less negative reduction potential of the reduced low‐coordinate iron formazanate complex leads to distinctive reactivity with formation of a new N−I bond that is not seen with the β‐diketiminate analogue. Thus, the storage of an electron on the supporting ligand changes the redox potential and enhances certain reactivity.
A Balance between van der Waals and Cation–π Interactions Stabilizes Hydrophobic Assemblies
Authors: Zhan Yi‐Yang , Kojima Tatsuo , Koide Takuya , Tachikawa Masanori , Hiraoka Shuichi
Published: April 2018

A thermally highly stable molecular self‐assembly (nanocube) in water, the decomposition temperature of which is 415 K, was developed by designing a gear‐shaped amphiphile (GSA) with an indented hydrophobic surface, even though the nanocube is stabilized only by van der Waals (vdW) and cation–π interactions as well as the hydrophobic effect. The introduction of an electron‐donating substituent in one of the benzene rings of the GSA increased the decomposition temperature by 12 K, which is due to the stronger cation–π interactions between the benzene ring and positively charged pyridinium rings and tighter molecular meshing between the GSAs in the nanocube. The position of the substituent introduced in the benzene ring greatly affects the thermal stability of the nanocubes, and this indicates that both vdW (molecular meshing) and cation–π interactions are crucial for improving the thermal stability of the hydrophobic assemblies.
Designing the Backbone of Hexasilabenzene Derivatives with a High Unimolecular Kinetic Stability
Authors: Sumiya Yosuke , Maeda Satoshi
Published: April 2018

It is an important subject to theoretically predict the kinetic stability of transient species. In this study, we have studied the kinetic stability of hexasilabenzene Si6H6 and its derivatives, that is, decasilanaphthalene Si10H8 and Li‐substituted hexasilabenzene Si6Li6, theoretically by the artificial force induced reaction (AFIR) method combined with the rate constant matrix contraction (RCMC) method. Molecular design was further conducted to extend the unimolecular lifetime of hexasilabenzene derivatives. Although both Si10H8 and Si6Li6 were shown to possess shorter lifetimes than Si6H6, we found that the lifetimes of Si6Li6 changed depending on arrangements of Li atoms around the monocyclic Si6 backbone. Based on this knowledge, we found that a compound of an atomic composition Si6H4Li2 with a planar, monocyclic Si6 backbone has a relatively long unimolecular lifetime. Moreover, substitution of the two Li atoms by Na atoms further increased the lifetime.
Fluorescent DNA‐Templated Silver Nanoclusters from Silver(I)‐Mediated Base Pairs
Authors: Léon J. Christian , González‐Abradelo Darío , Strassert Cristian A. , Müller Jens
Published: April 2018

Silver nanoclusters (AgNCs) stabilized by double‐stranded DNA (dsDNA) are of special interest because the duplex structures provide rigidity and chirality that can be transferred to the metal clusters. This work reports fluorescent AgNCs obtained from dsDNA templates containing artificial ligand‐derived nucleobases. They are compared with fluorescent AgNCs obtained from DNA templates containing C:C mismatches (C, cytosine). Towards this end, the new metal‐mediated Im−AgI−C base pair composed of imidazole (Im) and cytosine was introduced into dsDNA and reduced to form AgNCs. The clusters were characterized by UV/Vis, fluorescence and circular dichroism spectroscopy. The AgNCs form chiral aggregates with dsDNA. Their optical properties are highly sequence‐dependent. As a result, a simple method to detect a cytosine insertion into a run of cytosine residues in a duplex is proposed using the human CDH1 gene as an example.
Halogens – light emission and fire
Authors: Weiß Dieter , Täuscher Eric , Brandl† Herbert
Published: April 2018

Die Stoffgruppe der Halogene stellen, bedingt durch ihre Eigenschaften, Reaktivität und Ubiquität ein zentrales Thema in jedem Chemieunterricht dar. Nach zahlreichen Debatten in den letzten Jahren über die Sicherheit bei den Experimenten mit Halogenen soll dieser Artikel eindrucksvolle, didaktisch wertvolle, sichere und funktionierende Reaktionen mit den Halogenen aufzeigen. Licht oder Feuer erzeugende Reaktionen, haben sich als besonders einprägsam herausgestellt, so dass eben solche hier ausgewählt wurden. Dabei wird explizit auf den sicheren Umgang mit Halogenen eingegangen.
Improvement in clinical outcomes of patients with heart failure and active cocaine use after β‐blocker therapy
Authors: Lopez Persio D. , Akinlonu Adedoyin , Mene‐Afejuku Tuoyo O. , Dumancas Carissa , Saeed Mohammed , Cativo Eder H. , Visco Ferdinand , Mushiyev Savi , Pekler Gerald
Published: April 2018

Background

Cocaine use has a high prevalence in the United States and can be associated with significant cardiovascular disease, even in asymptomatic users. β‐Adrenergic receptor hyperactivation is the underlying pathophysiologic pathway of cocaine cardiotoxicity. β‐Blocker therapy is controversial in patients with active cocaine use.

Hypothesis

β‐Blocker therapy is associated with clinical improvement in patients with heart failure despite active cocaine use.

Methods

In a single‐center, retrospective chart analysis, patients with newly diagnosed heart failure and active cocaine use who had been started on β‐blocker therapy were reviewed. The New York Heart Association (NYHA) functional class and the left ventricular ejection fraction (LVEF) were recorded at baseline and after 12 monthsnthsnths of β‐blocker use. Patients were excluded if they had been on prior β‐blocker therapy, had other reasons for volume overload, had chronic kidney disease stages G4 or G5, or had a life expectancy <12 months.

Results

Thirty‐eight patients were identified; most were African American males. A statistically significant improvement was found in both NYHA functional class (P < 0.0001) and LVEF (P < 0.0001) after 12 months of β‐blocker therapy. No major adverse cardiovascular events occurred in this population.

Conclusions

β‐Blocker use in cocaine users with heart failure with a reduced ejection fraction is associated with a lower NYHA functional class and a higher LVEF at 12‐month follow‐up. No major adverse cardiovascular events were observed.
Early effects of empagliflozin on exercise tolerance in patients with heart failure: A pilot study
Authors: Núñez Julio , Palau Patricia , Domínguez Eloy , Mollar Anna , Núñez Eduardo , Ramón Jose María , Miñana Gema , Santas Enrique , Fácila Lorenzo , Górriz Jose Luis , Sanchis Juan , Bayés‐Genís Antoni
Published: April 2018

Background

Sodium‐glucose linked transporter 2 inhibition recently emerged as a promising therapy for reducing the risk of heart failure (HF) in patients with type 2 diabetes mellitus (T2DM). However, there is a lack of data endorsing its role in symptomatic HF patients. We sought to evaluate the short‐term effects of empagliflozin on maximal exercise capacity in these patients.

Hypothesis

We postulate tretament with empagliflozin may improve functional capacity in patients with T2DM and established HF.

Methods

Nineteen T2DM patients with symptomatic HF were prospectively included and underwent cardiopulmonary exercise testing before and 30 days after initiation of empagliflozin therapy. A mixed‐effects model for repeated measures was used.

Results

Median patient age was 72 years (interquartile range, 60–79 years); 42.1% were in New York Heart Association class III. Baseline mean (± SD) peak oxygen consumption (peak VO2) was 10.9 ± 4.0 mL/min/kg. Peak VO2 increased significantly at 30 days (∆: +1.21 [0.66 to 1.76] mL/min/kg; P < 0.001). A significant improvement in ventilatory efficiency during exercise, 6‐minute walking distance, and quality of life, and a reduction in antigen carbohydrate 125, were also found. Estimated glomerular filtration rate and natriuretic peptides did not significantly change.

Conclusions

In this pilot study, empagliflozin was associated with 1‐month improvement in exercise capacity in T2DM patients with symptomatic HF. This beneficial effect was also found for other surrogates of severity.
Prognostic value of exercise capacity among patients with treated depression: The Henry Ford Exercise Testing (FIT) Project
Authors: Ahmed Amjad M. , Qureshi Waqas T. , Sakr Sherif , Blaha Michael J. , Brawner Clinton A. , Ehrman Jonathan K. , Keteyian Steven J. , Al‐Mallah Mouaz H.
Published: April 2018

Background

Exercise capacity is associated with survival in the general population. Whether this applies to patients with treated depression is not clear.

Hypothesis

High exercise capacity remains associated with lower risk of all‐cause mortality (ACM) and nonfatal myocardial infraction (MI) among patients with treated depression.

Methods

We included 5128 patients on antidepressant medications who completed a clinically indicated exercise stress test between 1991 and 2009. Patients were followed for a median duration of 9.4 years for ACM and 4.5 years for MI. Exercise capacity was estimated in metabolic equivalents of tasks (METs). Cox proportional hazards regression models were used.

Results

Patients with treated depression who achieved ≥12 METs (vs those achieving <6 METs) were younger (age 46 ± 9 vs 61 ± 12 years), more often male (60% vs 23%), less often black (10% vs 27%), and less likely to be hypertensive (51% vs 86%), have DM (9% vs 38%), or be obese (11% vs 36%) or dyslipidemic (45% vs 54%). In the fully adjusted Cox proportional hazard regression model, exercise capacity was associated with a lower ACM (HR per 1‐MET increase in exercise capacity: 0.82, 95% CI: 0.79–0.85, P < 0.001) and nonfatal MI (HR: 0.92, 95% CI: 0.87–0.97, P = 0.004).

Conclusions

Exercise capacity had an inverse association with both ACM and nonfatal MI in patients with treated depression, independent of cardiovascular risk factors. These results highlight the potential impact of assessing exercise capacity to identify risk, as well as promoting an active lifestyle among treated depression patients.
The Effects of Operational Parameters on the Iron(III) Uptake by Micro‐Algae Dunaliella salina
Authors: Anghel Lilia , Duca Gheorghe , Cepoi Liliana , Iatco Iulia , Rudi Ludmila , Erhan Raul Victor
Published: April 2018

The uptake of Fe(III) by living cells of unicellular green algae Dunaliella salina ions is investigated. The effects of operational conditions such as contact time, biomass concentration, initial pH, and initial Fe(III) concentration on iron uptake are studied. The time profile of the Fe(III) uptake by living cells of D. salina shows a time lag in the first 15 min, which is associated with the production of metal chelating agents. In addition, it is found that the optimum pH for maximal iron uptake is 8. At optimal conditions, the uptake is increasing gradually along with the increase of biomass concentration. Furthermore, the uptake increased with the rising of the initial metal ion concentration. Dry samples of iron free and iron containing biomass of D. salina are analyzed using Fourier‐transform infrared (FTIR) spectroscopy. Comparison of the obtained FTIR spectra revealed the presence of amino, carboxylic, hydroxylic, phosphate and sulphonate groups of the lipids, proteins and polysaccharides localized at the cell surface, which are involved in the process of Fe(III) acquisition.
Interactions of β tubulin isotypes with glutathione in differentiated neuroblastoma cells subject to oxidative stress
Authors: Guo Jiayan , Kim Hong Seok , Asmis Reto , Ludueña Richard F.
Published: April 2018

Microtubules are a major component of the neuronal cytoskeleton. Tubulin, the subunit protein of microtubules, is an α/β heterodimer. Both α and β exist as families of isotypes, whose members are encoded by different genes and have different amino acid sequences. The βII and βIII isotypes are very prominent in the nervous system. Our previous work has suggested that βII may play a role in neuronal differentiation, but the role of βIII in neurons is not well understood. In the work reported here, we examined the roles of the different β‐tubulin isotypes in response to glutamate/glycine treatment, and found that both βII and βIII bind to glutathione in the presence of ROS, especially βIII. In contrast, βI did not bind to glutathione. Our results suggest that βII and βIII, but especially βIII, may play an important role in the response of neuronal cells to stress. In view of the high levels of βII and βIII expressed in the nervous system it is conceivable that these tubulin isotypes may use their sulfhydryl groups to scavenge ROS and protect neuronal cells against oxidative stress.
Molecular signatures in hepatocellular carcinoma: A step toward rationally designed cancer therapy
Authors: Erstad Derek J. , Fuchs Bryan C. , Tanabe Kenneth K.
Published: April 2018

Molecular characterization of hepatocellular carcinoma (HCC) has greatly improved our understanding of disease pathogenesis. Mutational analysis, RNA and microRNA expression profiling, and epigenetic characterization have revealed common aberrations in oncogenes and tumor suppressors that correlate with disease biology and serve as a guide for the rational design of targeted therapies. These approaches have also led to the discovery of novel targets, including mutations in isocitrate dehydrogenase and chromatin remodeling enzymes. With the advent of immunotherapy, RNA expression profiling of the tumor microenvironment has identified a subset of HCC with high lymphocyte infiltration that may benefit from checkpoint inhibitor therapy. Molecular signatures thus capture the biology of a tumor, providing a supplement to current staging schema, which are based on tumor size and number, for more accurate prognostication of recurrence risk and survival. Molecular signatures may also be used to guide interventional therapy by defining those most suitable for transplantation or locoregional therapy rather than surgical resection. Finally, a multiomics approach involves the aggregation and analysis of multiple signatures for a more comprehensive characterization of pathogenic mechanisms. This broader approach attempts to address issues with signaling pathway cross‐talk and redundancy, which have greatly limited the potential value of targeted therapies to date. Cancer 2018. © 2018 American Cancer Society.
Patient Protection and Affordable Care Act Medicaid expansion and gains in health insurance coverage and access among cancer survivors
Authors: Nikpay Sayeh S. , Tebbs Margaret G. , Castellanos Emily H.
Published: April 2018

BACKGROUND

The Patient Protection and Affordable Care Act extends Medicaid coverage to millions of low‐income adults, including many survivors of cancer who were unable to purchase affordable health insurance coverage in the individual health insurance market.

METHODS

Using data from the 2011 to 2015 Behavioral Risk Factor Surveillance System, the authors compared changes in coverage and health care access measures for low‐income cancer survivors in states that did and did not expand Medicaid.

RESULTS

The study population of 17,381 individuals included adults aged 18 to 64 years, and was predominantly female, white, and unmarried. The authors found a relative reduction in the uninsured rate of 11.7 percentage points and a relative increase in the probability of having a personal physician of 5.8 percentage points. Stratifying by whether states expanded Medicaid by 2015, the authors found that relative gains in coverage and access were larger among those individuals residing in states with expanded Medicaid compared with those residing in nonexpansion states.

CONCLUSIONS

The results of the current study suggest that the Patient Protection and Affordable Care Act Medicaid expansion has improved coverage and access for cancer survivors. Cancer 2018;124:2645‐52. © 2018 American Cancer Society.
Mesoporous Shell@Macroporous Core Aluminosilicates as Sustainable Nanocatalysts for Direct N‐alkylation of Amines
Authors: Sunil Sekhar Anandakumari C. , Ashokkumar Anumol Erumpukuthickal , Cygnet Choorapoikayil T. , Vidhya Lakshmi Saseendranpillai , Deepak Francis Leonard , Vinod Chathakudath P.
Published: April 2018

Aluminosilicate spheres with a macroporous core and mesoporous shell (Si/Al ratio of 11) is synthesised by a sol‐gel method utilizing cetyltrimethyl ammonium bromide (CTAB) as a structure directing agent in basic medium. The selective incorporation of aluminium in the silica matrix results in the formation of aluminosilicates with an overall acidity of 0.32 mmol/g with interconnected pores. Direct N‐alkylation reaction is a prototype of C−N bond formation reaction and meso‐ macroporous aluminosilicate is shown to catalyze this reaction with excellent yield. The catalyst is tested and found sustainable for five catalytic cycles even without any high temperature regeneration step.
Blockchain‐based fair three‐party contract signing protocol for fog computing
Authors: Huang Hui , Li Kuan‐Ching , Chen Xiaofeng
Published: April 2018

Fog computing is a new computing paradigm that can provide flexible resources and services at the edge of network. It is an extension of cloud computing and usually cooperated with cloud computing. Therefore, end users, fog nodes, and cloud servers can form a three‐layer service model in practical application. In this model, they should have an agreement on a service contract, which contains every party's rights and obligations before the beginning of the service. However, due to lack of trust, it will suffer from some fairness problems during signing a service contract. Contract signing protocol allows two or more mutual distrust entities to sign a predefined digital contract in a fair and effective way. In this paper, we propose a fair three‐party contract signing protocol based on the primitive of blockchain, which can be applied to the scenario of fog computing. Our proposed construction allows the participants to sign a contract in a fair way without the involvement of an arbitrator. Moreover, the privacy of the contract content can be preserved on the public chain. Finally, we realize the proposed protocol through the private blockchain and provide the experimental simulation that analyzes the efficiency and effectiveness.