bluuebunny/crossref_metadata_2025 huggingface dataset:
Diaminodicyanochinone – Fluoreszenzfarbstoffe mit hohem Dipolmoment und Elektronenakzeptor‐Eigenschaften
Authors: Rietsch Philipp , Witte Felix , Sobottka Sebastian , Germer Gregor , Krappe Alexander , Güttler Arne , Sarkar Biprajit , Paulus Beate , Resch‐Genger Ute , Eigler Siegfried
Published: April 2019

Fluoreszenzfarbstoffe werden in verschiedenen Forschungsbereichen eingesetzt, darunter Solarzellen, lichtemittierende Dioden, Reporter für Assays oder Bioimaging‐Studien. Ein zusätzliches hohes Dipolmoment ebnet den Weg zu nichtlinearer Optik und Polaritätsempfindlichkeit. Die Redoxaktivität ermöglicht es zudem, photophysikalische Eigenschaften der Moleküle zu verändern. Diaminodicyanochinon‐Derivate besitzen hohe Dipolmomente, aber nur geringe Fluoreszenzquantenausbeuten und galten daher bislang nicht als Fluoreszenzfarbstoffe. Wir untersuchen in dieser Arbeit die Fluoreszenzeigenschaften von Diaminodicyanochinonen mit einem kombiniert theoretisch‐experimentellen Ansatz und leiten Moleküle mit einer Fluoreszenz‐Quantenausbeute von über 90 % ab. Die Diaminodicyanochinon‐Einheit bietet chemische Vielseitigkeit und kann in neuartige molekulare Architekturen mit einzigartigen photophysikalischen Eigenschaften integriert werden.
Aurophilic Interactions in the Self‐Assembly of Gold Nanoclusters into Nanoribbons with Enhanced Luminescence
Authors: Wu Zhennan , Du Yonghua , Liu Jiale , Yao Qiaofeng , Chen Tiankai , Cao Yitao , Zhang Hao , Xie Jianping
Published: April 2019

Aurophilic interactions (AuI⋅⋅⋅AuI) are crucial in directing the supramolecular self‐assembly of many gold(I) compounds; however, this intriguing chemistry has been rarely explored for the self‐assembly of nanoscale building blocks. Herein, we report on studies on aurophilic interactions in the structure‐directed self‐assembly of ultrasmall gold nanoparticles or nanoclusters (NCs, <2 nm) using [Au25(SR)18]− (SR=thiolate ligand) as a model cluster. The self‐assembly of NCs is initiated by surface‐motif reconstruction of [Au25(SR)18]− from short SR‐[AuI‐SR]2 units to long SR‐[AuI‐SR]x (x>2) staples accompanied by structure modification of the intrinsic Au13 kernel. Such motif reconstruction increases the content of AuI species in the protecting shell of Au NCs, providing the structural basis for directed aurophilic interactions, which promote the self‐assembly of Au NCs into well‐defined nanoribbons in solution. More interestingly, the compact structure and effective aurophilic interactions in the nanoribbons significantly enhance the luminescence intensity of Au NCs with an absolute quantum yield of 6.2 % at room temperature.
Regio‐ and Enantioselective Iridium‐Catalyzed N‐Allylation of Indoles and Related Azoles with Racemic Branched Alkyl‐Substituted Allylic Acetates
Authors: Kim Seung Wook , Schempp Tabitha T. , Zbieg Jason R. , Stivala Craig E. , Krische Michael J.
Published: April 2019

Cyclometallated π‐allyliridium C,O‐benzoates modified with (S)‐tol‐BINAP, which are stable to air, water, and SiO2, catalyze highly enantioselective N‐allylations of indoles and related azoles. This reaction complements previously reported metal‐catalyzed indole allylations in that complete levels of N versus C3 and branched versus linear regioselectivity are observed.
Diaminodicyanoquinones: Fluorescent Dyes with High Dipole Moments and Electron‐Acceptor Properties
Authors: Rietsch Philipp , Witte Felix , Sobottka Sebastian , Germer Gregor , Krappe Alexander , Güttler Arne , Sarkar Biprajit , Paulus Beate , Resch‐Genger Ute , Eigler Siegfried
Published: April 2019

Fluorescent dyes are applied in various fields of research, including solar cells and light‐emitting devices, and as reporters for assays and bioimaging studies. Fluorescent dyes with an added high dipole moment pave the way to nonlinear optics and polarity sensitivity. Redox activity makes it possible to switch the molecule's photophysical properties. Diaminodicyanoquinone derivatives possess high dipole moments, yet only low fluorescence quantum yields, and have therefore been neglected as fluorescent dyes. Here we investigate the fluorescence properties of diaminodicyanoquinones using a combined theoretical and experimental approach and derive molecules with a fluorescence quantum yield exceeding 90 %. The diaminodicyanoquinone core moiety provides chemical versatility and can be integrated into novel molecular architectures with unique photophysical features.
Continuous Zeolite MFI Membranes Fabricated from 2D MFI Nanosheets on Ceramic Hollow Fibers
Authors: Min Byunghyun , Yang Shaowei , Korde Akshay , Kwon Yeon Hye , Jones Christopher W. , Nair Sankar
Published: April 2019

High‐quality 2D MFI nanosheet coatings were prepared on α‐alumina hollow fiber supports by vacuum filtration and then transformed into molecular sieving membranes by two sequential hydrothermal treatments. This processing method eliminates the need for specially engineered silica‐based support materials that have so far been necessary to allow the formation of functional membranes from 2D MFI nanosheets. The sequential steps enhance adhesion of the membrane on the fiber support, fill in nanoscale gaps between the 2D nanosheets, and preserve the desirable (0k0) out‐of‐plane orientation without the need of any support engineering or modification. The membrane exhibits high performance for separation of n‐butane from i‐butane, and for other technologically important hydrocarbon separations. The present findings have strong implications on strategies for obtaining thin, highly selective zeolite membranes from 2D zeolites in a technologically scalable manner.
Transformation of a [4+6] Salicylbisimine Cage to Chemically Robust Amide Cages
Authors: Bhat Avinash S. , Elbert Sven M. , Zhang Wen‐Shan , Rominger Frank , Dieckmann Michael , Schröder Rasmus R. , Mastalerz Michael
Published: April 2019

In recent years, interest in shape‐persistent organic cage compounds has steadily increased, not least because dynamic covalent bond formation enables such structures to be made in high to excellent yields. One often used type of dynamic bond formation is the generation of an imine bond from an aldehyde and an amine. Although the reversibility of the imine bond formation is advantageous for high yields, it is disadvantageous for the chemical stability of the compounds. Amide bonds are, in contrast to imine bonds much more robust. Shape‐persistent amide cages have so far been made by irreversible amide bond formations in multiple steps, very often accompanied by low yields. Here, we present an approach to shape‐persistent amide cages by exploiting a high‐yielding reversible cage formation in the first step, and a Pinnick oxidation as a key step to access the amide cages in just three steps. These chemically robust amide cages can be further transformed by bromination or nitration to allow post‐functionalization in high yields. The impact of the substituents on the gas sorption behavior was also investigated.
Effects of hydrothermal treatment on oxygen functional groups and pyrolysis characteristics of a vitrinite‐rich low rank coal
Authors: Zhu Chuan , Xie Qiang , Zhong Jinlong , Guo Hao , Zhang Yuhong
Published: April 2019

A vitrinite‐rich low rank coal (BSR) with high alkali and alkaline metal species contents from China was treated by hydrothermal treatment over a temperature range of 200°C to 300°C. The transformation in physicochemical structure was investigated. The pyrolysis behaviors and product distribution were discussed. Meanwhile, the effect of inorganic elements derived from hydrothermal liquid waste on coal pyrolysis was also explored. The results show that after hydrothermal treatment, some inorganic elements (e.g., Na and Cl) as well as the equilibrium moisture decreased significantly. A time/temperature delay effect for the decomposition of newly formed carboxyl acids from ion exchange of carboxylates is revealed. With the increasing treatment temperature, atomic ratio of O/C decreases gradually, whereas H/C shows a trend of first increasing below 240°C and then decreasing. The pyrolysis activation energy increases from 38.51 kJ mol−1 of BSR to 52.01 kJ mol−1 of sample treated at 300°C. Hydrothermal treatment with temperature below 260°C could promote tar yield by fixed‐bed pyrolysis, while not by Gray–King assay. Furthermore, the inorganic elements in hydrothermal liquid waste increased the pyrolysis activation energy and resulted in lower tar yield and higher gas yield. Compare with char from BSR, mean pore size of chars from treated coals increased, and corresponding specific surface area decreased dramatically.
Modified ethylene‐propylene‐diene elastomer (EPDM)‐contained silicone rubber/ethylene‐propylene‐diene elastomer (EPDM) blends: Effect of composition and electron beam crosslinking on mechanical, heat shrinkability, electrical, and morphological properties
Authors: Ashokrao Fuke Chandan , Anna Mahanwar Prakash , Ray Chowdhury Subhendu
Published: April 2019

In this investigation, a gamma radiation‐induced methacrylic acid (MAA)‐grafted ethylene‐propylene‐diene elastomer (EPDM) was used as a third component (g‐EPDM) in silicone rubber (SiR)/ethylene‐propylene‐diene elastomer (EPDM) blends. These blends were electron beam (EB) crosslinked. The effect of blend composition, the presence of g‐EPDM, and EB crosslinking on the mechanical, heat shrinkability, electrical, and morphological properties of SiR/EPDM blends have been studied. To investigate the effect of grafted EPDM (g‐EPDM), 10 wt % of g‐EPDM was added to immiscible SiR/EPDM blends. Both silicone and EPDM are blended in different proportions (70:30 and 30:70) with and without g‐EPDM followed by compression molding. To improve the properties and investigate the crosslinkability of binary and ternary blends further, the SiR/EPDM blends were irradiated by electron beam at different doses (50, 100, and 150 kGy). The gel content was found to increase with EPDM content, the presence of g‐EPDM, and radiation dose. The addition of g‐EPDM led to improvement of tensile properties (tensile strength, Young's modulus, percentage elongation, and toughness), electrical properties, and shrinkability of blends. EB crosslinking further enhanced the above properties. Surface morphology (SEM) revealed that the presence of g‐EPDM and the incorporation of EB crosslinking improved the above properties of blends. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47787.
Mechanical properties of 3D parts fabricated by fused deposition modeling: Effect of various fillers in polylactide
Authors: Gao Xia , Zhang Daijun , Qi Shunxin , Wen Xiangning , Su Yunlan
Published: April 2019

Weak mechanical strength and serious mechanical anisotropy are two key limiting factors for three‐dimensional (3D) parts prepared by fused deposition modeling (FDM) in industrial applications. In this work, we investigated the relationships between mechanical properties and surface quality of FDM parts with the properties of materials used. Three kinds of polylactide (PLA) filaments, composed of the same PLA matrix but different fillers (carbon fibers and talc), were used to prepare FDM specimens. Due to the nature of FDM process, FDM parts exhibited tensile properties weaker and more anisotropic than their injection‐molding counterparts. The presence of fillers affected the tensile properties of FDM parts, especially the degree of mechanical anisotropy. It is found that the interlayer bond governing the mechanical performance of FDM parts was improved since the fillers added in the polymer materials facilitates the molecular diffusion across the bond interface. Also, the surface quality of FDM parts varied with fillers. Neat PLA parts exhibited surface quality superior to the 3D parts printed with composites filaments. This work is believed to provide highlights on the development of polymer composites filament and improvement of mechanical properties of FDM parts. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47824.
Towards Self‐Regulated Bioprocessing: A Compact Benchtop Bioreactor System for Monitored and Controlled 3D Cell and Tissue Culture
Authors: de Bournonville Sébastien , Lambrechts Toon , Vanhulst Johan , Luyten Frank P. , Papantoniou Ioannis , Geris Liesbet
Published: April 2019

Bioreactors are crucial tools for the manufacturing of living cell‐based tissue engineered products. However, to reach the market successfully, higher degrees of automation, as well as a decreased footprint still need to be reached. In this study, the use of a benchtop bioreactor for in vitro perfusion culture of scaffold‐based tissue engineering constructs is assessed. A low‐footprint benchtop bioreactor system is designed, comprising a single‐use fluidic components and a bioreactor housing. The bioreactor is operated using an in‐house developed program and the culture environment is monitored by specifically designed sensor ports. A gas‐exchange module is incorporated allowing for heat and mass transfers. Titanium‐based scaffolds are seeded with human periosteum‐derived cells and cultured up to 3 weeks. The benchtop bioreactor constructs are compared to benchmark perfusion systems. Live/Dead stainings, DNA quantifications, glucose consumption, and lactate production assays confirm that the constructs cultured in the benchtop bioreactor grew similarly to the benchmark systems. Manual regulation of the system set points enabled efficient alteration of the culture environment in terms of temperature, pH, and dissolved oxygen. This study provides the necessary basis for the development of low‐footprint, automated, benchtop perfusion bioreactors and enables the implementation of active environment control.
EWOD silicon biosensor for multiple nucleic acids analysis
Authors: Petralia Salvatore , Motta Daniele , Conoci Sabrina
Published: April 2019

In this paper, a miniaturized biosensor containing 96 silicon microchambers electroloaded with nano‐volumes of liquid (EW‐chip) is presented. The liquid electroloading is achieved by the appropriate modulation of interface properties. The surface chemistries have been studied to guarantee effective interface properties for both electrowetting on dielectric actuation and biocompatibility versus biochemical reactions. The silicon microchambers are 200 nl in volume and are connected to a specific system of electrodes able to deliver liquid sample on each well. The device also integrates temperature sensors and heaters to perform biochemical reactions. On that, the effectiveness of this device has been successfully proven towards the nucleic acids detection via real‐time polymerase chain reaction amplification. Hepatitis B virus genome target has been used to assess the device performance. Results show very uniform amplification over the 96 microchambers without any cross‐contamination process. These features make this system a very appealing potential solution for genetic point‐of‐care devices where a high level of parallelism of analysis is required.
Photosynthetic generation of heterologous terpenoids in cyanobacteria
Authors: Betterle Nico , Melis Anastasios
Published: April 2019

The work aims to convert the secondary slow metabolism of the terpenoid biosynthetic pathway into a primary activity in cyanobacteria and to generate heterologous products using these photosynthetic microorganisms as cell factories. Case study is the production of the 10‐carbon monoterpene β‐phellandrene (PHL) in Synechocystis sp. PCC 6803 (Synechocystis). Barriers to this objective include the slow catalytic activity of the terpenoid metabolism enzymes that limit rates and yield of product synthesis and accumulation. “Fusion constructs as protein overexpression vectors” were applied in the overexpression of the geranyl diphosphate synthase (GPPS) and β‐phellandrene synthase (PHLS) genes, causing accumulation of GPPS up to 4% and PHLS up to 10% of the total cellular protein. Such GPPS and PHLS protein overexpression compensated for their slow catalytic activity and enabled transformant Synechocystis to constitutively generate 24 mg of PHL per g biomass (2.4% PHL:biomass, w‐w), a substantial improvement over earlier yields. The work showed that a systematic overexpression, at the protein level, of the terpenoid biosynthetic pathway genes is a promising approach to achieving high yields of prenyl product biosynthesis, on the way to exploiting the cellular terpenoid metabolism for commodity product generation.
Invisible signals from the underground: A practical method to investigate the effect of microbial volatile organic compounds emitted by rhizobacteria on plant growth
Authors: del Rosario Cappellari Lorena , Chiappero Julieta , Banchio Erika
Published: April 2019

Rhizobacteria that colonize plant roots and promote plant growth are referred to as plant growth‐promoting rhizobacteria, and this can stimulate plant growth either indirectly or directly. Volatile organic compounds (VOCs) emitted by rhizobacteria have the capacity to promote plant growth as well as perform biocontrol of fungal pathogens. The microbial volatile organic compounds (mVOCs) are characterized by a low molecular weight and a high vapor pressure, which facilitate evaporation and diffusion at normal temperatures and at above‐ground and below‐ground pressures. mVOCs can travel far from the point of production through the atmosphere, porous soils and liquids, thereby making them ideal infochemicals for mediating interspecific interactions. However, knowledge about the biological and ecological roles of microbial VOCs is still limited compared with that of plant VOCs. Here, we describe a simple and inexpensive laboratory class aimed at biotechnology or soil microbiology students, which uses techniques to increase their understanding of the mechanisms of plant growth promoting rhizobacteria and also illustrate the effects of mVOCs emitted by rhizobacteria on plant growth promotion, as well as evaluating their potential as a biocontrol. The laboratory class is divided into two sessions: an initial 3‐hour experimental session and a second 2‐hour analytical one. The experimental session involves two separate experiments: one of which is dedicated to illustrating the effect of mVOCs on plant growth parameters, while the second explores the capacity of VOCs as a biocontrol. Also, the class provides students with an opportunity to perform useful assays, draw conclusions from their results, and discuss possible extensions of the study. © 2019 International Union of Biochemistry and Molecular Biology, 47(4):388–393, 2019.
Focus on Epithelialized Palatal Grafts. Part 3: Methods to Enhance Patient Comfort at Palatal Donor Sites
Authors: Berridge Joshua P. , Johnson Thomas M. , Cheng Albert W. , Swenson Dane T. , Miller Preston D.
Published: April 2019

Introduction

Postoperative discomfort is a documented complication of the epithelialized palatal graft (EPG) procedure, and the expectation of an unpleasant patient experience may cause some practitioners to avoid EPG altogether. However, EPG affords distinct advantages in a variety of clinical situations, and the postoperative discomfort associated with the procedure can be minimized.

Case Series

Three generally and periodontally healthy patients with gingival recession defects and minimal zones of attached gingiva received mandibular anterior EPG procedures. In all cases, collagen membranes were trimmed to fit the palatal donor sites and sutured in place. Two patients reported minimal donor site discomfort at any time point. One patient with large bilateral donor sites reported moderate palatal discomfort limited to the first postoperative week. All patients reported overall positive treatment experiences.

Conclusions

Placement of a resorbable collagen membrane at large EPG harvest sites appears to limit topical irritation of the wound and may substantially improve patient comfort postoperatively. Combining local and systemic measures to minimize patient discomfort may render EPG procedures very tolerable for patients. Controlled clinical trials comparing patient‐centered outcomes following EPG harvest with and without collagen membrane placement appear warranted.
Direct access valve‐in‐valve implantation for management of complex valvulopathy
Authors: Kossar Alexander P. , Borger Michael , George Isaac
Published: April 2019

The management of bioprosthetic structural valve degeneration requires complex surgical or transcatheter re‐intervention for which many high‐risk patients are not considered candidates. Here, we describe a technique for a direct surgical access valve‐in‐valve implantation in patients with complex bioprosthetic valvulopathy for whom standard surgical valve replacement and percutaneous interventions were high‐risk and contraindicated, respectively.
Diagnostic performance of quantitative flow ratio in prospectively enrolled patients: An individual patient‐data meta‐analysis
Authors: Westra Jelmer , Tu Shengxian , Campo Gianluca , Qiao Shubin , Matsuo Hitoshi , Qu Xinkai , Koltowski Lukasz , Chang Yunxiao , Liu Tommy , Yang Junqing , Andersen Birgitte Krogsgaard , Eftekhari Ashkan , Christiansen Evald Høj , Escaned Javier , Wijns William , Xu Bo , Holm Niels Ramsing
Published: April 2019

Objectives

We aimed to provide robust performance estimates for quantitative flow ratio (QFR) in assessment of intermediary coronary lesions.

Background

Angiography‐based functional lesion assessment by QFR may appear as a cost saving and safe approach to expand the use of physiology‐guided percutaneous coronary interventions. QFR was proven feasible and showed good diagnostic performance in mid‐sized off‐line and on‐line studies with fractional flow reserve (FFR) as reference standard.

Methods

We performed a collaborative individual patient‐data meta‐analysis of all available prospective studies with paired assessment of QFR and FFR using the CE‐marked QFR application. The main outcome was agreement of QFR and FFR using a two‐step analysis strategy with a multilevel mixed model accounting for study and center level variation.

Results

Of 16 studies identified, four studies had prospective enrollment and provided patient level data reaching a total of 819 patients and 969 vessels with paired FFR and QFR: FAVOR Pilot (n = 73); WIFI II (n = 170); FAVOR II China (n = 304) and FAVOR II Europe‐Japan (n = 272). We found an overall agreement (mean difference 0.009 ± 0.068, I2 = 39.6) of QFR with FFR. The diagnostic performance was sensitivity 84% (95%CI: 77–90, I2 = 70.1), specificity 88% (95%CI: 84–91, I2 = 60.1); positive predictive value 80% (95%CI: 76–85, I2 = 33.4), and negative predictive value 95% (95%CI: 93–96, I2 = 75.9).

Conclusions

Diagnostic performance of QFR was good with FFR as reference in this meta‐analysis of high quality studies. QFR could provide an easy, safe, and cost‐effective solution for functional evaluation of coronary artery stenosis.
Remote ‘Imidazole’ Based Ruthenium(II) p‐Cymene Precatalyst for Selective Oxidative Cleavage of C−C Multiple Bonds
Authors: Dutta Manali , Bania Kusum Kumar , Pratihar Sanjay
Published: April 2019

The dual role of remote ‘imidazole’ attached with the precatalyst [(p‐cymene)RuII(L)Y]+ (L=2‐(4‐substituted‐phenyl)‐1H‐imidazo[4,5‐f][1,10] phenanthroline, Y=chloride/solvent) was explored for the selective oxidative cleavage of C−C multiple bonds to acetals/aldehydes. The presence of ‘imidazole’ in the precatalysts was found to be useful for the activation of oxidant and release of p‐cymene from the precatalysts, which in turn was not effective without the ‘imidazole’ moiety. The mechanistic aspects of the precatalyst were evaluated from spectroscopic, kinetic, and few other controlled experiments. The loss of p‐cymene is the key step for the reaction and found to be faster in solvated precatalyst, [(p‐cymene)RuII(L)(MeOH)]++ and thus showed 3–4‐fold more effective as compared to [(p‐cymene)RuII(L)Cl]+.
Catalytic Aerobic Phenol Homo‐ and Cross‐Coupling Reactions with Copper Complexes Bearing Redox‐Active Guanidine Ligands
Authors: Schön Florian , Kaifer Elisabeth , Himmel Hans‐Jörg
Published: April 2019

Due to their large importance in synthetic chemistry, catalytic C−C coupling reactions of phenols are currently intensively studied. Herein, new copper catalysts for the C−C coupling reaction of phenols using dioxygen as a green oxidizing reagent are reported. By using redox‐active guanidine ligands, the activity as well as chemoselectivity in the cross‐coupling reaction of non‐complementary phenols (between an electron‐rich phenol and a less nucleophilic second phenol) is significantly improved. Based on the collected data for several test reactions, a reaction mechanism is proposed.
Synergistic Catalysis: Highly Enantioselective Cascade Reaction for the Synthesis of Dihydroacridines
Authors: Meninno Sara , Meazza Marta , Yang Jung Woon , Tejero Tomas , Merino Pedro , Rios Ramon
Published: April 2019

The first stereoselective synthesis of dihydroacridines through synergistic catalysis, achieving the final target compounds with good to excellent yields and good to excellent enantioselectivities and diastereoselectivities, is reported. The synergistic approach consists in the activation of substituted quinolines with a Lewis acid catalyst that react in a cascade fashion with activated enals in the iminium form. Mechanistic calculations support a consecutive Michael–aldol reaction, followed by dehydration.
An Oxalate‐Bridged Binuclear Iron(III) Ionic Liquid for the Highly Efficient Glycolysis of Polyethylene Terephthalate under Microwave Irradiation
Authors: Cot Sergi , Leu Meike K. , Kalamiotis Alexis , Dimitrakis Georgios , Sans Victor , de Pedro Imanol , Cano Israel
Published: April 2019

An oxalate‐bridged binuclear iron(III) ionic liquid combined with an imidazolium based cation, (dimim)2[Fe2Cl4(μ‐ox)], was synthesized and characterized by a wide range of techniques. This halometallate ionic liquid was active in catalyzing the depolymerization of polyethylene terephthalate (PET) by glycolysis, under conventional and microwave‐assisted heating conditions. Both methodologies were very selective towards the production of bis(2‐hydroxyethyl)terephthalate (BHET). The employment of microwave heating proved beneficial in terms of time and energy saving when compared to the use of thermal heating. Indeed, dielectric spectroscopy studies revealed that the binuclear iron‐containing ionic liquid exhibits an excellent heating response under an electromagnetic field. The catalyst provided quantitative conversions to BHET in the glycolysis of post‐consumer PET bottles in only 3 h through microwave heating, as compared to 80 % conversion after 24 h under conventional heating.
Mg‐Ion Inversion in MgO@MgO−Al2O3 Oxides: The Origin of Basic Sites
Authors: Hiremath Vishwanath , Kwon Hyuk Jae , Jung In‐Sun , Kwon Soonchul , Kwon Sung Hyun , Lee Seung Geol , Lee Hyun Chul , Seo Jeong Gil
Published: April 2019

Although MgO−Al2O3 is well known as having a spinel structure, the inversion of which occurs by exchange of the trivalent (Al3+) and divalent (Mg2+) cations, little analytical study of the degree of inversion has been carried out. This study concerns a simple methodology to identify the inversion by solid‐state NMR spectroscopy, whereby its correlation with the CO2 capture capacity of MgO‐rich MgO@MgO−Al2O3 spinel structures is verified. Through 27Al and 25Mg NMR spectroscopy, temperature‐programmed CO2 desorption, and thermogravimetric analysis, higher inversion is found to occur at low Mg/Al ratios and the inversion is found to decrease as the Mg/Al ratio increases. Moreover, the degree of inversion correlates with CO2 sorption, which is associated with the medium‐strength basic sites induced by formation of the unsaturated O2− species. These results will open new pathways to exploit defects in complex oxides beyond spinels and their derivatives for desired applications. This demonstration of MgO−Al2O3 for CO2 sorption can contribute to the design of future CO2 sorbents.
Benign epithelioid peripheral nerve sheath tumour arising in the rectum: A cytological and histological description
Authors: Foo Tiffany Siang Ying , Laycock Andrew
Published: April 2019

A 57‐year old man presented with a 3.6 cm submucosal rectal cystic mass detected on colonoscopy and MRI. The lesion was deroofed, with rectal cyst fluid and cyst wall received for examination. Smears contained atypical cells occurring singly and in small aggregates, with epithelioid and spindled cells with hyperchromatic nuclei. Occasional cells exhibited intranuclear cytoplasmic inclusions. The concurrent histopathology specimen from the rectal cyst wall showed good correlation with the cytologic findings. The lesion was confined to the muscularis propria, with predominantly epithelioid cells and occasional spindled forms arranged in sheets, nests, and trabeculae with intervening fibrillary and fibrous stroma. Mitotic figures were scant, with no atypical mitoses or necrosis. An extensive immunohistochemical panel was performed, showing strong and diffuse nuclear and cytoplasmic staining with S100 and moderate to strong intensity nuclear staining with SOX10, in keeping with a benign epithelioid peripheral nerve sheath tumour. The patient remains well 3 years following diagnosis, and two subsequent biopsies at the site show no evidence of recurrent disease. We herein provide the first cytologic description of this lesion, with histopathologic correlation and a brief review of other differential diagnostic possibilities.
Asperteramide A, an Unusual N‐Phenyl‐Carbamic Acid Methyl Ester Trimer Isolated from the Coral‐Derived Fungus Aspergillus Terreus
Authors: Liu Mengting , He Yan , Shen Ling , Anbari Weaam Hasan Al , Li Huaqiang , Wang Jianping , Qi Changxing , Hu Zhengxi , Zhang Yonghui
Published: April 2019

Asperteramide A, an unusual N‐phenyl‐carbamic acid methyl ester trimer, was isolated and identified from the coral‐derived fungus Aspergillus terreus. The deceptive and indistinguishable NMR signals caused by three N‐phenyl‐carbamic acid methyl ester subunits located in different spatial environments created great challenge for the identification of its planar structure, but recrystallization ultimately afforded a suitable crystal for the X‐ray diffraction experiment, which enabled its final structure determination. The plausible biosynthetic pathway of 1 mainly involved in the successive Friedel–Crafts reactions. Additionally, compound 1 showed significant antibacterial activity against seven microbial pathogens [ESBL‐producing Escherichia coli, Acinetobacter baumannii, Pseudomonas aeruginosa, Klebsiella pneumoniae, methicillin‐resistant Staphylococcus aureus, Enterococcus faecalis, Candida albicans] with MIC values ranging from 2 to 64 µg/mL.
Toward Improving the Areal Energy Density of Lithium–Sulfur Batteries with Ultramicroporous Carbon–Sulfur Composite Electrodes
Authors: Helen M. , Fichtner Maximilian , Reddy M. Anji
Published: April 2019

Sulfur possesses high specific capacity (1672 mA h g−1) and high specific energy (2600 Wh kg−1), which makes it attractive as a cathode material for lithium–sulfur batteries. However, the areal energy density of sulfur electrodes is usually low due to an excess amount of inactive materials, mostly carbon, in the electrode composite. Typically, the electrode layers must be thin to achieve good specific capacity and cyclic stability. This further reduces the areal capacities, and it is challenging to design high areal density sulfur electrodes. Herein, the possibility of achieving high areal energy density by using ultramicroporous carbon–sulfur (UMC‐S) composite electrodes is investigated. For this purpose, the weight of sulfur per area is systematically varied by varying the amount of UMC‐S, and its electrochemical performance with respect to current density, cycling voltage window, electrolyte amount, and effect of temperature on cycling is investigated. A sulfur loading of up to 9.7 mg cm−2 and areal capacities above 4.5 mAh cm−2 are attained. The results indicate that a high areal energy density can be achieved with UMC‐S electrodes, however, at lower current rates. Higher current rates can be achieved by reducing the particle size and by improving the intrinsic electronic conductivity of the UMC host.
Bone Morphogenetic Protein 9 Is a Paracrine Factor Controlling Liver Sinusoidal Endothelial Cell Fenestration and Protecting Against Hepatic Fibrosis
Authors: Desroches‐Castan Agnès , Tillet Emmanuelle , Ricard Nicolas , Ouarné Marie , Mallet Christine , Belmudes Lucid , Couté Yohann , Boillot Olivier , Scoazec Jean‐Yves , Bailly Sabine , Feige Jean‐Jacques
Published: April 2019

Bone morphogenetic protein 9 (BMP9) is a circulating factor produced by hepatic stellate cells that plays a critical role in vascular quiescence through its endothelial receptor activin receptor‐like kinase 1 (ALK1). Mutations in the gene encoding ALK1 cause hereditary hemorrhagic telangiectasia type 2, a rare genetic disease presenting hepatic vessel malformations. Variations of both the circulating levels and the hepatic mRNA levels of BMP9 have been recently associated with various forms of hepatic fibrosis. However, the molecular mechanism that links BMP9 with liver diseases is still unknown. Here, we report that Bmp9 gene deletion in 129/Ola mice triggers hepatic perisinusoidal fibrosis that was detectable from 15 weeks of age. An inflammatory response appeared within the same time frame as fibrosis, whereas sinusoidal vessel dilation developed later on. Proteomic and mRNA analyses of primary liver sinusoidal endothelial cells (LSECs) both revealed that the expression of the LSEC‐specifying transcription factor GATA‐binding protein 4 was strongly reduced in Bmp9 gene knockout (Bmp9‐KO) mice as compared with wild‐type mice. LSECs from Bmp9‐KO mice also lost the expression of several terminal differentiation markers (Lyve1, Stab1, Stab2, Ehd3, Cd209b, eNos, Maf, Plvap). They gained CD34 expression and deposited a basal lamina, indicating that they were capillarized. Another main characteristic of differentiated LSECs is the presence of permeable fenestrae. LSECs from Bmp9‐KO mice had a significantly reduced number of fenestrae. This was already observable in 2‐week‐old pups. Moreover, we could show that addition of BMP9 to primary cultures of LSECs prevented the loss of their fenestrae and maintained the expression levels of Gata4 and Plvap. Conclusion: Taken together, our observations show that BMP9 is a key paracrine regulator of liver homeostasis, controlling LSEC fenestration and protecting against perivascular hepatic fibrosis.
Non‐V600E BRAF mutations and EGFR signaling pathway in colorectal cancer
Authors: Osumi Hiroki , Shinozaki Eiji , Wakatsuki Takeru , Suenaga Mitsukuni , Ichimura Takashi , Ogura Mariko , Takahari Daisuke , Ooki Akira , Suzuki Takeshi , Ota Yumiko , Nakayama Izuma , Chin Keisho , Miki Yoshio , Yamaguchi Kensei
Published: April 2019

The Raf murine sarcoma viral oncogene homolog B (BRAFV600E) mutation (MT) in metastatic colorectal cancer (CRC) is a well‐known prognostic indicator and a negative predictive biomarker for antiepidermal growth factor receptor (EGFR) treatment. However, the clinical characteristics and significance of BRAFnon‐V600E MTs remain unclear. Here, we evaluated the clinical characteristics of BRAFnon‐V600E MTs vs. those of other MTs in the EGFR signaling pathway, including BRAFV600E. Consecutive CRC patients in our institute from June 2012 to November 2013 were enrolled in our study. Multiplex genotyping of the EGFR pathway was performed with archival samples using a Luminex Assay for BRAFV600E/BRAFnon‐V600E, KRAS/NRAS exons 2–4, and phosphatidylinositol‐4,5‐bisphosphate 3‐kinase, catalytic subunit alpha (PIK3CA). We analyzed correlations among the MT profiles, clinical data and primary tumor locations in CRC. All statistical analyses were performed using R software. CRC samples (824) from 374 (45.4%) male and 450 (54.6%) female patients were analyzed, of which 154 (18.7%), 202 (24.5%), 270 (32.8%) or 198 (24.0%) had Stages I, II, III or IV or recurrent CRC, respectively. The frequencies of BRAFV600E/BRAFnon‐V600E, KRAS (including exons 2–4), NRAS and PIK3CA MTs were 5.3/1.7, 41.4, 3.3 and 9.6%, respectively. The characteristics of patients with the BRAFV600E MT were an age of ≥65 years old, a right‐sided primary tumor location, poorly differentiated histology and an advanced disease stage. In contrast, the characteristics of patients with BRAFnon‐V600E MTs were a left‐sided primary tumor location and well‐differentiated histology. BRAFnon‐V600E MTs were relatively rare and showed different characteristics compared to the BRAFV600E MT. These results may contribute to future precision medicine.
Expression of miR‐486‐5p and its signiﬁcance in lung squamous cell carcinoma
Authors: Yang Sheng , Sui Jing , Liu Tong , Wu Wenjuan , Xu Siyi , Yin Lihong , Pu Yuepu , Zhang Xiaomei , Zhang Yan , Shen Bo , Liang Geyu
Published: April 2019

Lung squamous cell carcinoma (LUSC) is one of the main histological types of lung cancer with high mortality. The role of microRNA‐486‐5p in LUSC remains unclear. In the current study, the aim was to explore miR‐486‐5p expression and its role in LUSC. The miR‐486‐5p expression was significantly low‐expressed in patients with LUSC from The Cancer Genome Atlas database, which was further confirmed in the Gene Expression Omnibus database, patients’ tissues, different cell lines by quantitative real‐time polymerase chain reaction, and the high‐throughput gene sequencing data of lung tissues of mice after a long‐term B(a)P exposure. The meta‐analysis was performed to evaluate the expression and diagnosis power of miR‐486‐5p (standard mean difference = −2.25; 95% confidence interval: −3.47 to −1.03; P = 0.0003; area under curve = 0.9082). Functional enrichment analysis revealed the potential function of miR‐486‐5p in LUSC using gene set enrichment analysis and clusterProfiler package in R software. At last, the hub genes (PTEN, TEK, PIK3R1, PPM1B, SMAD2, and SPTA1) of miR‐486‐5p were verified. In conclusion, miR‐486‐5p may be a LUSC antioncogene, playing an important role to serve as a biomarker in LUSC.
Downregulation of long noncoding RNA LINC00683 associated with unfavorable prognosis in prostate cancer based on TCGA
Authors: Liu Yunfeng , Yang Bishan , Su Youmin , Xiang Qiuling , Li Quhuan
Published: April 2019

Prostate cancer (PCa) is the third most common reason of cancer‐related deaths in men. Accumulating evidence has shown that dysregulation of long noncoding RNAs (lncRNAs) is closely related to cancer initiation and development. Although large numbers of lncRNAs have been discovered, knowledge regarding their function and physiological/pathological significance remains limited. In this study, we aimed to reveal functional lncRNAs and identify prognosis‐related RNAs in PCa by analyzing data from The Cancer Genome Atlas (TCGA). To achieve this, an lncRNA‐mRNA coexpression network was constructed by weighted correlation network analysis. Additionally, a subnetwork was extracted from this weighted correlation network, and seven lncRNAs were identified as core nodes. Further Kaplan‐Meier survival analysis showed that three lncRNAs (LINC00683, LINC00857, and FENDRR) were significantly downregulated in PCa samples, and there was a strong positive correlation with patient survival. Importantly, LINC00683 has not been fully reported as related with PCa. Additionally, gene set enrichment analysis indicated that LINC00683 might be involved in cancer‐related pathways such as the Wnt pathway. Based on the findings of this study, lncRNA LINC00683 is likely to provide a new diagnostic biomarker and therapeutic target for future PCa treatments.
Islet cells are the source of Wnts that can induce beta‐cell proliferation in vitro
Authors: Maschio Daniela A. , Matheus Valquíria A. , Collares‐Buzato Carla B.
Published: April 2019

Wnt proteins act mainly as paracrine signals regulating cell proliferation and differentiation. The canonical Wnt pathway has recently been associated with pancreas development and the onset of type 2 diabetes in rodent and human but the underlying mechanisms are still unclear. The aim of this work was threefold: (a) to screen for Wnt expressed by murine pancreas/islet cells, (b) to investigate whether the Wnt gene expression profile can be changed in hyperplastic islets from type 2 prediabetic mice (fed a high‐fat diet), and (c) to verify whether soluble factors (namely Wnts) released by pancreatic islets affect insulin secretion and proliferation of a beta‐cell line in vitro condition. The majority of the Wnt subtypes are expressed by islet cells, such as Wnts 2, 2b, 3, 3a, 4, 5a, 5b, 6, 7a, 7b, 8a, 8b, 9a, 9b, and 11, while in the whole pancreas homogenates were found the same subtypes, except Wnts 3, 6, 7a, and 7b. Among all the Wnts, the Wnts 3a and 5b showed a significantly increased gene expression in hyperplastic islets from prediabetic mice compared with those from control mice. Furthermore, we observed that coculture with hyperplastic or nonhyperplastic islets did not change the secretory function of the mouse insulinoma clone 6 (MIN6) beta cells but induced a significant increase in cell proliferation in this lineage, which was partially blocked by the IWR‐1 and IWP‐2 Wnt inhibitors. In conclusion, we demonstrated that murine pancreas/islet cells can secrete Wnts, and that islet‐released Wnts may participate in the regulation of beta‐cell mass under normal and prediabetic conditions.
Adipocyte lineage differentiation potential of MSCs isolated from reaming material
Authors: Toosi Shirin , Esmaeilzadeh Zohreh , Naderi‐Meshkin Hojjat , Heirani‐Tabasi Asieh , Peivandi Mohammad Taghi , Behravan Javad
Published: April 2019

Mesenchymal stem cells (MSCs) obtained from various sources have been used for different therapeutic applications including tissue regeneration. Reamer/irrigator/aspirator (RIA) has been increasingly used in recent years for the derivation of MSCs. Here in this investigation we have comparatively analyzed MSCs obtained from iliac crest bone marrow (ICBM) and RIA for their morphology, cluster determinant (CD) markers, and adipogenic differentiation capacity. MSCs were isolated, cultured, and purified from both sources and then flow cytometric studies were performed to study their characteristics. The differentiation potential of RIA and ICBM was examined by an Oil Red O staining protocol. Moreover, the tissue‐specific markers related to adipogenesis were analyzed by real‐time polymerase chain reaction (RT‐PCR). The cells were cultured in the relevant induction medium and then adipogenic lineage differentiation was tested and confirmed for all MSC preparations. Additionally, analysis by flow cytometer was indicative of RIA derived MSCs (RIA‐MSCs) having a more homogenous population than ICBM derived MSCs. The RIA‐MSCs differentiation toward adipogenic lineage was more efficient compared with ICBM‐MSCs. Direct comparative analysis of RIA to ICBM‐MSCs indicated that the RIA‐MSCs had a higher potential toward adipocyte lineage differentiation compared with ICBM‐MSCs.
Spontaneous differentiation of periodontal ligament stem cells into myofibroblast during ex vivo expansion
Authors: Iwasaki Kengo , Komaki Motohiro , Akazawa Keiko , Nagata Mizuki , Yokoyama Naoki , Watabe Tetsuro , Morita Ikuo
Published: April 2019

Periodontitis is characterized by the chronic inflammation and destruction of tooth‐supporting tissues. Periodontal ligament stem cell (PDLSC) is the mesenchymal stem cell (MSC) population isolated from periodontal ligament, which is the key tissue for regeneration of periodontal tissues. Although transplantation of PDLSCs is proposed as novel regenerative therapy, limited information is available, regarding the characteristic change of PDLSCs during ex vivo expansion. In this study, we encountered morphological change of PDLSCs during standard cell culture and aimed to investigate the change of PDLSCs in stem cell characteristics and to search for the culture condition to maintain stem cell properties. Characteristics of PDLSCs were examined using in vitro osteoblast and adipocyte differentiation. Myofibroblast differentiation was confirmed using immunohistochemistry and collagen gel contraction assay. Replicative senescence was examined by β‐gal staining. PDLSCs changed their morphology from spindle to flat and wide during ex vivo expansion. After the morphological change, PDLSCs showed several features of myofibroblast including extensive stress fiber formation, contraction activity, and myofibroblast marker expression. Upon the morphological change, osteoblastic and adipocyte differentiation capacity were reduced and expression of stem cell‐related genes were decreased. β‐Gal staining was not always correlated with the morphological change of PDLSCs. Moreover, exogenous addition of bFGF and PDGF‐BB served to maintain spindle shape and osteoblastic differentiation potential of PDLSCs. This study demonstrates that spontaneous differentiation of PDLSCs during ex vivo expansion and may provide the important information of cell culture condition of PDLSCs for clinical use.
A toolkit for genetics providers in follow‐up of patients with non‐diagnostic exome sequencing
Authors: Zastrow Diane B. , Kohler Jennefer N. , Bonner Devon , Reuter Chloe M. , Fernandez Liliana , Grove Megan E. , Fisk Dianna G. ,   Undiagnosed Diseases Network, Yang Yaping , Eng Christine M. , Ward Patricia A. , Bick David , Worthey Elizabeth A. , Fisher Paul G. , Ashley Euan A. , Bernstein Jonathan A. , Wheeler Matthew T.
Published: April 2019

There are approximately 7,000 rare diseases affecting 25–30 million Americans, with 80% estimated to have a genetic basis. This presents a challenge for genetics practitioners to determine appropriate testing, make accurate diagnoses, and conduct up‐to‐date patient management. Exome sequencing (ES) is a comprehensive diagnostic approach, but only 25%–41% of the patients receive a molecular diagnosis. The remaining three‐fifths to three‐quarters of patients undergoing ES remain undiagnosed. The Stanford Center for Undiagnosed Diseases (CUD), a clinical site of the Undiagnosed Diseases Network, evaluates patients with undiagnosed and rare diseases using a combination of methods including ES. Frequently these patients have non‐diagnostic ES results, but strategic follow‐up techniques identify diagnoses in a subset. We present techniques used at the CUD that can be adopted by genetics providers in clinical follow‐up of cases where ES is non‐diagnostic. Solved case examples illustrate different types of non‐diagnostic results and the additional techniques that led to a diagnosis. Frequent approaches include segregation analysis, data reanalysis, genome sequencing, additional variant identification, careful phenotype‐disease correlation, confirmatory testing, and case matching. We also discuss prioritization of cases for additional analyses.