bluuebunny/crossref_metadata_2025 huggingface dataset:
Exercise intensity‐dependent immunomodulatory effects on encephalomyelitis
Authors: Fainstein Nina , Tyk Reuven , Touloumi Olga , Lagoudaki Roza , Goldberg Yehuda , Agranyoni Oryan , Navon‐Venezia Shiri , Katz Abram , Grigoriadis Nikolaos , Ben‐Hur Tamir , Einstein Ofira
Published: August 2019

Background

Exercise training (ET) has beneficial effects on multiple sclerosis and its animal model experimental autoimmune encephalomyelitis (EAE). However, the intensity‐dependent effects of ET on the systemic immune system in EAE remain undefined.

Objective

(1) To compare the systemic immune modulatory effects of moderate versus high‐intensity ET protocols in protecting against development of EAE; (2) To investigate whether ET affects autoimmunity selectively, or causes general immunosuppression.

Methods

Healthy mice performed moderate or high‐intensity treadmill running programs. Proteolipid protein (PLP)‐induced transfer EAE was utilized to examine ET effects specifically on the systemic immune system. Lymph node (LN)‐T cells from trained versus sedentary donor mice were transferred to naïve recipients and EAE severity was assessed, by clinical assessment and histopathological analysis. LN‐T cells derived from donor trained versus sedentary PLP‐immunized mice were analyzed in vitro for proliferation assays by flow cytometry analysis and cytokine and chemokine receptor gene expression using real‐time PCR. T cell‐dependent immune responses of trained versus sedentary mice to the nonautoantigen ovalbumin and susceptibility to Escherichia coli‐induced acute peritonitis were examined.

Results

High‐intensity training in healthy donor mice induced significantly greater inhibition than moderate‐intensity training on proliferation and generation of encephalitogenic T cells in response to PLP‐immunization, and on EAE severity upon their transfer into recipient mice. High‐intensity training also inhibited LN‐T cell proliferation in response to ovalbumin immunization. E. coli bacterial counts and dissemination were not affected by training.

Interpretation

High‐intensity training induces superior effects in preventing autoimmunity in EAE, but does not alter immune responses to E. coli infection.
All‐Dielectric Active Terahertz Photonics Driven by Bound States in the Continuum
Authors: Han Song , Cong Longqing , Srivastava Yogesh Kumar , Qiang Bo , Rybin Mikhail V. , Kumar Abhishek , Jain Ravikumar , Lim Wen Xiang , Achanta Venu Gopal , Prabhu Shriganesh S. , Wang Qi Jie , Kivshar Yuri S. , Singh Ranjan
Published: August 2019

The remarkable emergence of all‐dielectric meta‐photonics governed by the physics of high‐index dielectric materials offers a low‐loss platform for efficient manipulation and subwavelength control of electromagnetic waves from microwaves to visible frequencies. Dielectric metasurfaces can focus electromagnetic waves, generate structured beams and vortices, enhance local fields for advanced sensing, and provide novel functionalities for classical and quantum technologies. Recent advances in meta‐photonics are associated with the exploration of exotic electromagnetic modes called the bound states in the continuum (BICs), which offer a simple interference mechanism to achieve large quality factors (Q) through excitation of supercavity modes in dielectric nanostructures and resonant metasurfaces. Here, a BIC‐driven terahertz metasurface with dynamic control of high‐Q silicon supercavities that are reconfigurable at a nanosecond timescale is experimentally demonstrated. It is revealed that such supercavities enable low‐power, optically induced terahertz switching and modulation of sharp resonances for potential applications in lasing, mode multiplexing, and biosensing.
Synergistic Effects between MXenes and Ni Chains in Flexible and Ultrathin Electromagnetic Interference Shielding Films
Authors: Wang Shi‐Jun , Li Dian‐Sen , Jiang Lei
Published: August 2019

Developing high‐performance electromagnetic interference (EMI) shielding materials has become increasingly important along with the upcoming 5G communication era and the boom of wearable devices. However, the large thickness and poor mechanical properties of most of EMI shielding materials cannot satisfy the above critical requirements. Here, flexible and ultrathin poly(vinylidene fluoride) (PVDF)/MXene/Ni chain composite films are fabricated. Interestingly, by combining quasi‐1D Ni chains and 2D MXenes, the average EMI shielding effectiveness of the PVDF/MXene/Ni chain composite films can reach 19.3 dB with only 0.10 mm thickness, and increases to 34.4 dB with 0.36 mm thickness. Besides, the tensile strength, Young's modulus, and toughness of the PVDF/MXene/Ni chain composite films are 41.9 ± 1.6 MPa, 1.18 ± 0.007 GPa, and 2.9 ± 0.08 MJ m−3, respectively. All of which are better than when using MXenes or Ni chains alone at the same loading. It is attributed to synergistic effects induced by unique 3D network constituted by MXenes and Ni chains. Moreover, the possible synergistic mechanisms for enhanced EMI shielding and mechanical properties are discussed. This work offers a promising solution for EMI shielding challenges in modern smaller and smaller wearable devices.
Iron(III)‐Catalyzed Hydration of Unactivated Internal Alkynes in Weak Acidic Medium, under Lewis Acid‐Assisted Brønsted Acid Catalysis
Authors: Antenucci Achille , Flamini Piergiorgio , Fornaiolo Marco Valerio , Di Silvio Sergio , Mazzetti Sara , Mencarelli Paolo , Salvio Riccardo , Bassetti Mauro
Published: August 2019

Alkylarylalkynes are converted with full regioselectivity into the corresponding arylketones by formal hydration of the triple bond under weak acidic conditions, at times and temperatures (≤95 °C) comparable to those used for terminal alkynes. The process catalyzed by Fe2(SO4)3nH2O in glacial acetic acid exhibits good functional group compatibility, including that with bulky triple bond substituents, and can be extended to the one‐pot transformation of aryltrimethylsilylacetylenes into acetyl derivatives via a desilylation‐hydration sequence. The overall reactivity pattern along with proton affinity data indicate that the triple bond is activated by proton transfer rather than by π‐interaction with the metal ion. This mechanistic feature, at variance with that of noble metal catalysts, accounts for the total regioselectivity and the insensitivity to steric hindrance exhibited by the Fe2(SO4)3nH2O/AcOH catalytic system.

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Field‐Effect Transistors Based on 2D Organic Semiconductors Developed by a Hybrid Deposition Method
Authors: Zhou Zhiwen , Wu Qisheng , Wang Sijia , Huang Yu‐Ting , Guo Hua , Feng Shien‐Ping , Chan Paddy Kwok Leung
Published: August 2019

Solution‐processed 2D organic semiconductors (OSCs) have drawn considerable attention because of their novel applications from flexible optoelectronics to biosensors. However, obtaining well‐oriented sheets of 2D organic materials with low defect density still poses a challenge. Here, a highly crystallized 2,9‐didecyldinaphtho[2,3‐b:2′,3′‐f]thieno[3,2‐b]thiophene (C10‐DNTT) monolayer crystal with large‐area uniformity is obtained by an ultraslow shearing (USS) method and its growth pattern shows a kinetic Wulff's construction supported by theoretical calculations of surface energies. The resulting seamless and highly crystalline monolayers are then used as templates for thermally depositing another C10‐DNTT ultrathin top‐up film. The organic thin films deposited by this hybrid approach show an interesting coherence structure with a copied molecular orientation of the templating crystal. The organic field‐effect transistors developed by these hybrid C10‐DNTT films exhibit improved carrier mobility of 14.7 cm2 V−1 s−1 as compared with 7.3 cm2 V−1 s−1 achieved by pure thermal evaporation (100% improvement) and 2.8 cm2 V−1 s−1 achieved by solution sheared monolayer C10‐DNTT. This work establishes a simple yet effective approach for fabricating high‐performance and low‐cost electronics on a large scale.
Women's experiences in early physical anthropology
Authors: Wilson Emily K.
Published: August 2019

At the establishment of the American Association of Physical Anthropologists in 1930, women comprised 2.4% of the total membership, and 9.7% a decade later. By 2014 ~70% of members were women. Despite these numbers, there are continued gender disparities within the discipline. While there is considerable interest in promoting equity, there is little documentation of the historical experiences of female anthropologists. This article introduces the women active in the discipline during the first decade of the Association, compiles descriptions of their experiences related to their treatment based on gender, and examines these historical perspectives in conjunction with documented trends of continuing gender disparities. A pattern is evident for these early anthropologists of receiving personal and financial discouragement during their education; experiencing discrimination in hiring, promotion, and pay; studying women and children as entrée into professional work; working within the federal government or military; leaving anthropology early in their careers; having their work credited to their male colleagues; experiencing additional limitations if they married; and outwardly downplaying their own experiences of sexism. This pattern is echoed in the experiences of female anthropologists today.
Understanding Hydrogen Bonding Interactions in Crosslinked Methylammonium Lead Iodide Crystals: Towards Reducing Moisture and Light Degradation Pathways
Authors: Nimens Wendy J. , Lefave Sarah J. , Flannery Laura , Ogle Jonathan , Smilgies Detlef‐M. , Kieber‐Emmons Matthew T. , Whittaker‐Brooks Luisa
Published: August 2019

Methylammonium lead halide perovskite‐based solar cells have demonstrated efficiencies as high as 24.2 %, highlighting their potential as inexpensive and solution‐processable alternatives to silicon solar cell technologies. Poor stability towards moisture, ultraviolet irradiation, heat, and a bias voltage of the perovskite layer and its various device interfaces limits the commercial feasibility of this material for outdoor applications. Herein, we investigate the role of hydrogen bonding interactions induced when metal halide perovskite crystals are crosslinked with alkyl or π‐conjugated boronic acid small molecules (‐B(OH)2). The crosslinked perovskite crystals are investigated under continuous light irradiation and moisture exposure. These studies demonstrate that the origin of the interaction between the alkyl or π‐conjugated crosslinking molecules is due to hydrogen bonding between the ‐B(OH)2 terminal group of the crosslinker and the I of the [PbI6]4− octahedra of the perovskite layer. Also, this interaction influences the stability of the perovskite layer towards moisture and ultraviolet light irradiation. Morphology and structural analyses, as well as IR studies as a function of aging under both dark and light conditions show that π‐conjugated boronic acid molecules are more effective crosslinkers of the perovskite crystals than their alkyl counterparts thus imparting better stability towards light and moisture degradation.
Directed Gas‐Phase Synthesis of Triafulvene under Single‐Collision Conditions
Authors: Thomas Aaron M. , Zhao Long , He Chao , Galimova Galiya R. , Mebel Alexander M. , Kaiser Ralf I.
Published: August 2019

The triafulvene molecule (c‐C4H4)—the simplest representative of the fulvene family—has been synthesized for the first time in the gas phase through the reaction of the methylidyne radical (CH) with methylacetylene (CH3CCH) and allene (H2CCCH2) under single‐collision conditions. The experimental and computational data suggest triafulvene is formed by the barrierless cycloaddition of the methylidyne radical to the π‐electron density of either C3H4 isomer followed by unimolecular decomposition through elimination of atomic hydrogen from the CH3 or CH2 groups of the reactants. The dipole moment of triafulvene of 1.90 D suggests that this molecule could represent a critical tracer of microwave‐inactive allene in cold molecular clouds, thus defining constraints on the largely elusive hydrocarbon chemistry in low‐temperature interstellar environments, such as that of the Taurus Molecular Cloud 1 (TMC‐1).
Brønsted Base Catalyzed One‐Pot Synthesis of Stereodefined Six‐Member Carbocycles Featuring Transient Trienolates and a Key Intramolecular 1,6‐Addition
Authors: Olaizola Olatz , Iriarte Igor , Zanella Giovanna , Gómez‐Bengoa Enrique , Ganboa Iñaki , Oiarbide Mikel , Palomo Claudio
Published: August 2019

A catalyst‐driven one‐pot reaction sequence is developed for the enantio‐ and diastereoselective synthesis of tetrasubstituted cyclohexenes from simple unsaturated ketones or thioesters. The method involves a tertiary amine/squaramide‐catalyzed α‐selective addition of transiently generated trienolates to nitroolefins, subsequent base‐catalyzed double bond isomerization, and an intramolecular (vinylogous) 1,6‐addition reaction, a rare key carbocyclization step that proceeded with essentially perfect stereocontrol.
Reducing Detrimental Defects for High‐Performance Metal Halide Perovskite Solar Cells
Authors: Ono Luis K. , Liu Shengzhong (Frank) , Qi Yabing
Published: August 2019

In several photovoltaic (PV) technologies, the presence of electronic defects within the semiconductor band gap limit the efficiency, reproducibility, as well as lifetime. Metal halide perovskites (MHPs) have drawn great attention because of their excellent photovoltaic properties that can be achieved even without a very strict film‐growth control processing. Much has been done theoretically in describing the different point defects in MHPs. Herein, we discuss the experimental challenges in thoroughly characterizing the defects in MHPs such as, experimental assignment of the type of defects, defects densities, and the energy positions within the band gap induced by these defects. The second topic of this Review is passivation strategies. Based on a literature survey, the different types of defects that are important to consider and need to be minimized are examined. A complete fundamental understanding of defect nature in MHPs is needed to further improve their optoelectronic functionalities.
Systematically Tuning the Electronic Structure of Gold Nanoclusters through Ligand Derivatization
Authors: Cirri Anthony , Morales Hernández Hanna , Kmiotek Christina , Johnson Christopher J.
Published: August 2019

While the ability to crystallize metal nanoclusters has revealed their geometric structure, the lack of a similarly precise measure of their electronic structure has hampered the development of synthetic design rules to precisely engineer their electronic properties. We track the evolution of highly‐resolved electronic absorption spectra of gold nanoclusters with precisely mass‐selected chemical composition in a controlled environment. Simple derivatization of the ligands yields larger spectral changes than varying the overall atomic composition of the cluster for two clusters with similar symmetry and size. The nominally metal‐localized HOMO–LUMO transition of these nanoclusters lowers in energy linearly with increasing electron donation from the exterior of the ligand shell for both cluster sizes. Very weak surface interactions, such as binding of He or N2, yield significant state‐dependent shifts, identifying states with significant interfacial character. These observations demonstrate a pathway for deliberate tuning of interfacial chemistry for chemical and technological applications.
Three‐dimensional bioprinting human cardiac tissue chips of using a painting needle method
Authors: Chikae Shohei , Kubota Akifumi , Nakamura Haruka , Oda Atsushi , Yamanaka Akihiro , Akagi Takami , Akashi Mitsuru
Published: August 2019

Three‐dimensional (3D) printers are attracting attention as a method for arranging and building cells in three dimensions. Bioprinting technology has potential in tissue engineering for the fabrication of scaffolds, cells, and tissues. However, these various printing technologies have limitations with respect to print resolution and due to the characteristics of bioink such as viscosity. We report a method for constructing of 3D tissues with a “microscopic painting device using a painting needle method” that, when used with the layer‐by‐layer (LbL) cell coating technique, replaces conventional methods. This method is a technique of attaching the high viscosity bioink to the painting needle tip and arranging it on a substrate, and can construct 3D tissues without damage to cells. Cell viability is the same before and after painting. We used this biofabrication device to construct 3D cardiac tissue (LbL‐3D Heart) using human‐induced pluripotent stem cell–derived cardiomyocytes. The constructed LbL‐3D Heart chips had multiple layers with a thickness of 60 µm, a diameter of 1.1 mm, and showed synchronous beating (50–60 beats per min). The aforementioned device and method of 3D tissue construction can be applied to various kinds of tissue models and would be a useful tool for pharmaceutical applications.
Multicenter study of carbon‐ion radiation therapy for nonsquamous cell carcinomas of the oral cavity
Authors: Ikawa Hiroaki , Koto Masashi , Demizu Yusuke , Saitoh Jun‐ichi , Suefuji Hiroaki , Okimoto Tomoaki , Ohno Tatsuya , Shioyama Yoshiyuki , Takagi Ryo , Hayashi Kazuhiko , Nemoto Kenji , Nakano Takashi , Kamada Tadashi
Published: August 2019

Background

The aim of this study was to evaluate the efficacy and safety of carbon‐ion radiation therapy for nonsquamous cell carcinomas of the oral cavity in a multicenter study.

Methods

Retrospective analysis of the clinicopathological features and outcomes of 76 patients with oral nonsquamous cell carcinomas with N0‐1 M0 status and were treated with carbon‐ion radiation therapy at four institutions in Japan between November 2003 and December 2014 was performed.

Results

Salivary gland carcinoma, mucosal melanoma, and three other carcinomas were found in 46, 27, and 3 patients, respectively. T1‐3, T4a, and T4b disease was diagnosed in 27, 18, and 31 patients, respectively. Median follow‐up period was 31.1 months (range, 3‐118 months). Three‐year local control, progression‐free survival, and overall survival of all patients were 86.8%, 63.1%, and 78.4%, respectively. Multivariate analysis showed T classification (T4) to be a significant independent poor prognostic factor for local control. Acute grade 3 mucositis was observed in 38 patients. Grades 3 and 4 late morbidities were observed in 9 and 4 patients, respectively. No grade 5 late toxicity was observed.

Conclusions

Oral nonsquamous cell carcinomas could be treated effectively, with acceptable toxicity, by carbon‐ion radiation therapy.
New Insights into Bioactive Compounds of Traditional Chinese Medicines for Insulin Resistance Based on Signaling Pathways
Authors: He Jian , Wang Hui , Vijg Jan
Published: August 2019

Type 2 diabetes is a serious metabolic disease as a long‐term threat to human health. Insulin resistance is not only the basis and major feature of type 2 diabetes, but also the main etiology of diseases such as hypertension, hyperlipidemia and coronary heart disease. It has been shown that Traditional Chinese Medicines (TCMs) play an important role in the treatment of type 2 diabetes, through attenuating insulin resistance, whereas the mechanism involved is not yet well understood. Therefore, it is important to elucidate the pharmacological mechanism of these bioactive compounds so that one can pave the way for the modernization of TCMs. In this review, we focus on the recent progresses of some bioactive ingredients from TCMs with different functional groups, which exhibit therapeutic potential for the treatment of diabetic insulin resistance. It is expected that this review can provide new references for developing TCM‐derived drugs against diabetes and insulin resistance in the future.
EGFR signaling pathway occupies an important position in cancer‐related downstream signaling pathways of Pyk2
Authors: Shen Ting , Guo Qiang
Published: August 2019

Proline‐rich tyrosine kinase 2 (Pyk2) is a member of focal adhesion kinase (FAK) non‐receptor tyrosine kinase family and has been found to promote cancer cell survival, proliferation, migration, invasion, and metastasis. Pyk2 takes part in different carcinogenic signaling pathways to promote cancer progression, including epidermal growth factor receptor (EGFR) signaling pathway. EGFR signaling pathway is a traditional carcinogenic signaling pathway, which plays a critical role in tumorigenesis and tumor progression. FAK inhibitors have been reported to fail to get the ideal anti‐cancer outcomes because of activation of EGFR signaling pathway. Better understanding of Pyk2 downstream targets and interconnectivity between Pyk2 and carcinogenic EGFR signaling pathway will help finding more effective targets for clinical anti‐cancer combination therapies. Thus, the interconnectivity between Pyk2 and EGFR signaling pathway, which regulates tumor development and metastasis, needs to be elucidated. In this review, we summarized the downstream targets of Pyk2 in cancers, focused on the connection between Pyk2 and EGFR signaling pathway in different cancer types, and provided a new overview of the roles of Pyk2 in EGFR signaling pathway and cancer development.
The Minor Impurity in Spent Ores of the “Siberian Metal”: Ruthenium Turns 175
Authors: Lewis David E.
Published: August 2019

The year 2019 commemorates the 175th anniversary of the discovery of the last of the platinum group metals, ruthenium. The discovery of this element is now attributed to the Russian chemist, Karl Karlovich Klaus (Carl Ernst Claus, 1796–1864). At that time, he was Professor of Chemistry at Kazan University, on the Volga River approximately 750 km (450 mi) east of Moscow. Klaus, whose laboratory practices violated practically every modern rule of laboratory safety, actually discovered the existence of the element in a crude extract of the spent platinum ores from the mint, by its odd taste and smell! Klaus and his discovery (including its defense against critics, who included Berzelius) are discussed here.
Original oder Fälschung?
Authors: Creydt Marina , Fischer Markus
Published: August 2019

Den Herausforderungen, denen Lebensmittelchemiker bereits heute und künftig wohl mehr begegnen, werden zunehmend umfassender und anspruchsvoller, da aufgrund der fortschreitenden Globalisierung die wirtschaftlichen Prozesse an Vernetzung gewinnen und zunehmend Fragen nach der Identität oder der Herkunft von Rohstoffen aufwerfen. Die in den letzten Jahren aufgedeckten Skandale der Lebensmittelbranche weisen darauf hin, dass das aktuelle System zur Sicherstellung der Authentizität von Lebensmitteln in spezifischen Bereichen bislang noch nicht vollständig ausreicht. Derzeit wird die Authentizität von Lebensmitteln bezüglich der Identität, Herkunft oder der Anbauweise durch den Gesetzgeber mit dem Prinzip der Rückverfolgbarkeit (traceability) angestrebt und üblicherweise auf der Basis von Dokumenten (z. B. Frachtpapiere, Lieferscheine) verfolgt. In der Praxis bietet die ausschließliche Überprüfung von Begleitpapieren jedoch häufig keinen ausreichenden Schutz, da sich diese leicht fälschen lassen. Um hier ein höheres Maß an Sicherheit zu gewährleisten und Irreführungen zu verhindern, werden analytische Strategien zur experimentellen Überprüfung der dokumentierten Angaben dringend benötigt. Die Etablierung von omics‐Technologien kann einen Beitrag dazu leisten, allerdings nur, wenn auch ein entsprechender Transfer in die direkte Anwendung sichergestellt wird. Dafür existieren bereits verschiedene Strategien und weitere Entwicklungen folgen, da neben den Verbrauchern und den staatlichen Untersuchungsämtern auch der produzierenden und vermarktenden Industrie daran gelegen ist, die Authentizität im Sinne qualitativ hochwertiger Lebensmittel sicherzustellen.
A novel generalized logistic dependent model to predict the presence of breast cancer based on biomarkers
Authors: Pham Hoang , Pham David H.
Published: August 2019

Breast cancer is the second most common cancer in women in the United States. With the revolution of the machine learning era, many researchers currently aim to find pathways and develop tools that may help to detect breast cancer early on in its development. We propose a novel generalized logistic dependent model with considerations of the dependence among selected biomarkers for breast cancer detection based on a set of nine biomarker predictors such as age, glucose, BMI, resistin, HOMA, MCP‐1, leptin, insulin, and adiponectin. Our research findings demonstrate that the proposed model has the potential to predict breast cancer in women just based on five biomarkers, ie, glucose, age, BMI, resistin, and MCP‐1. We also compare our model results to several other machine‐learning modeling approaches including SVM, logistic regression, random forest, and multiple regression analyses using various training data sets (60%, 70%, 80% of all data) and all the dataset. It shows that the inclusion of the dependence among those five predictors in the proposed model is worth the extra model complexity and effort for achieving a significant accuracy prediction level of breast cancer detection in women. Further work in broader validation of the conclusion of our study and exploring the ability for artificial intelligence (AI) to be able to bolster these predictions based on biomarkers are also discussed.
Conspecific olfactory preferences and interspecific divergence in odor cues in a chickadee hybrid zone
Authors: Van Huynh Alex , Rice Amber M.
Published: August 2019

Understanding how mating cues promote reproductive isolation upon secondary contact is important in describing the speciation process in animals. Divergent chemical cues have been shown to act in reproductive isolation across many animal taxa. However, such cues have been overlooked in avian speciation, particularly in passerines, in favor of more traditional signals such as song and plumage. Here, we aim to test the potential for odor to act as a mate choice cue, and therefore contribute to premating reproductive isolation between the black‐capped (Poecile atricapillus) and Carolina chickadee (P. carolinensis) in eastern Pennsylvania hybrid zone populations. Using gas chromatography–mass spectrometry, we document significant species differences in uropygial gland oil chemistry, especially in the ratio of ester to nonester compounds. We also show significant preferences for conspecific over heterospecific odor cues in wild chickadees using a Y‐maze design. Our results suggest that odor may be an overlooked but important mating cue in these chickadees, potentially promoting premating reproductive isolation. We further discuss several promising avenues for future research in songbird olfactory communication and speciation.
Towards Long Wavelength Absorbing Photodynamic Therapy Photosensitizers via the Extension of a [Ru(bipy)3]2+ Core
Authors: Karges Johannes , Blacque Olivier , Goldner Philippe , Chao Hui , Gasser Gilles
Published: August 2019

Complementary to classical treatment methods used against cancer, photodynamic therapy (PDT) has received increasing attention over the last years. PDT relies on the generation of reactive oxygen species (ROS) upon light irradiation to trigger cell death. As the wavelength employed during such treatments directly influences the light penetration depth and therefore the possibility to treat deep seated tumors or large tumors, research efforts have been made towards the development of photosensitizers (PSs) with an absorption in the phototherapeutic window (600–900 nm). To tackle this drawback, we report herein the preparation and characterization of new RuII‐containing PDT PSs, that are based on a [Ru(bipy)3]2+ core (1; bipy: 2,2′‐bipyridine) and that are extended with methyl groups (2) or vinyl dimethylamino groups (3). As anticipated with our design, we found a red‐shift of 65 nm of the maximum absorption of complex 3 in comparison to complex 1. In addition, we report on the in‐depth photophysical properties as well as (photo‐)cytotoxicity against cervical cancerous HeLa cells of the investigated compounds.
Half Sandwich Electron Deficient N,N′,N′′‐Triarylguanidinatoruthenium(II) Complexes: Syntheses, Reactivity Studies, and Structural Aspects
Authors: Kumar Robin , Ujjval Rishabh , Thirupathi Natesan
Published: August 2019

Three symmetrical N,N′,N′′‐triarylguanidinatoruthenium(II) complexes, [(η6‐p‐cymene)RuCl{κ2(N,N′)((ArN)2C‐N(H)Ar)}] (Ar = 2‐(CF3)C6H4 (1), 4‐(CF3)C6H4 (2) and 3,5‐(CF3)2C6H3 (3)) were isolated in good yields. The reaction of 3 with NaOAc, NaN3 and KSCN afforded [(η6‐p‐cymene)RuX{κ2(N,N′)((ArN)2C‐N(H)Ar)}] (X = OAc (4), N3 (5) and an admixture of SCN (6) and NCS (7)) respectively in very good yields. On the other hand, metathesis reaction of 3 with AgSbF6 in the presence of MeCN afforded [(η6‐p‐cymene)Ru(MeCN){κ2(N,N′)((ArN)2C‐N(H)Ar)}][SbF6] (8) in good yield. Complex 5 upon treatment with diethylacetylenedicarboxylate and bis(diphenylphosphanyl)acetylene separately afforded guanidinate(1–) complex, [(η6‐p‐cymene)Ru(N3C2(C(O)OEt)2){κ2(N,N′)((ArN)2C‐N(H)Ar)}] (9) and guanidinate(2–) complex, [(η6‐p‐cymene)Ru{κ2(N,N′)((ArN)2C=NAr)}(κ1P‐Ph2PC≡CPPh2)] (10) in good yields. The formation 9 vs. 10 is ascribed to the subtle difference in the electron richness of alkynes. The new complexes were characterized by analytical, IR and NMR spectroscopy and single‐crystal X‐ray diffraction. Complex 3 catalyses [3+2] cycloaddition reaction involving phenylacetylene and 4‐tolyl azide to afford an admixture of 1,4‐ and 1,5‐disubstituted 1,2,3‐triazoles, 23 and 24 in 99 % conversion.
Gold‐Catalyzed Functionalization of Semicarbazides with Terminal Alkynes to Achieve Substituted Semicarbazones
Authors: Zimin Dmitry P. , Dar'in Dmitry V. , Eliseeva Anastasiya A. , Novikov Alexander S. , Rassadin Valentin A. , Kukushkin Vadim Yu.
Published: August 2019

Gold‐catalyzed functionalization of semicarbazides (ArNHCONHNH2) with various terminal alkynes R2C≡CH (R2 = Alk or Ar) in the presence of Ph3PAuNTf2 (3 mol‐%) grants a range of substituted semicarbazones (16 examples; 64–93 %). This novel metal‐catalyzed coupling proceeds under mild conditions (PhCl, 60 °C) and demonstrates a high functional group tolerance; the reaction is sensitive to the electronic effects of the substituents in terminal alkynes. Inspection of XRD solid‐state structures of three obtained semicarbazones proved their dimerization via weak to moderate strength hydrogen bonding. The structures of the semicarbazones in solutions were studied by concentration dependent 1H NMR and 2D NMR and these experiments proved the presence of H‐bonds between two molecules. The nature and energy of H‐bonding (3.8–5.1 kcal/mol), degree of electron density delocalization, and rotational barriers via various bonds in the equilibrium model structures were studied by DFT calculations at the M06‐2X/6‐311++G** level of theory.
Hydrothermal Carbonization‐Derived Carbon from Waste Biomass as Renewable Pt Support for Fuel Cell Applications: Role of Carbon Activation
Authors: Schonvogel Dana , Nowotny Manuel , Woriescheck Tim , Multhaupt Hendrik , Wagner Peter , Dyck Alexander , Agert Carsten , Wark Michael
Published: August 2019

Pt catalysts in proton exchange membrane fuel cells (PEMFCs) typically use carbon blacks such as Vulcan (Vulcan is a registered trademark of the company Cabot Corporation) based on fossil sources. Thus, an important research task is using sustainable supports in PEMFCs. Hydrothermal carbonization (HTC) converts biomasses into chars, which are possible substitutes for fossil‐based carbons. Herein, a Pt catalyst derived from HTC of coconut shells is developed for catalysis of O2 reduction in acidic media. Thermal activation enlarges the specific surface area by factor of 7 to 546 m2 g−1 and generates electrical conductivity making the material suitable for catalysis. Pt particles of 1.8 ± 0.5 nm are distributed well on the activated carbon. Cyclic and CO stripping voltammetry show an electrochemical surface area (ECSA) of 69 ± 21 m2 gPt−1, almost identical to that of the commercial catalyst using Vulcan (69 ± 6 m2 gPt−1). Although ECSAs are highly comparable, the activity for O2 reduction is lower compared with the commercial catalyst. HTC‐derived carbon has a lower degree of graphitization, less functional oxygen groups on its surface, and a lower electrical conductivity than Vulcan. This suggests different Pt–support interactions.
Influence of High Aspect Ratio Lead‐Free Piezoelectric Fillers in Designing Flexible Fibrous Nanogenerators: Demonstration of Significant High Output Voltage
Authors: Bairagi Satyaranjan , Ali S. Wazed
Published: August 2019

Engineering a flexible, cost‐effective piezoelectric energy harvester with a higher piezoelectric performance, i.e., higher voltage and power density, is a great technical challenge nowadays. Herein, the same target is set to demonstrate a unique nanogenerator comprising nanorods (aspect ratio of ≈8.5) of lead‐free potassium sodium niobate (KNN) and poly(vinylidene fluoride) (PVDF) where further poling process is fully omitted. The unique dimension of the synthesized rods with minimal loading (only 3%) bestows, somewhat surprisingly, a negative effect on beta nucleation but subdues this effect by the significant contribution toward the piezoelectric response by self‐orienting the dipoles at the electrospinning process by itself. Thus, the approach resolves the unmet task of complicacy in poling both the molecular and ionic dipoles at the same electric field in a subsequent poling of the finally formed nanocomposite. The nanodevice shows a higher open‐circuit output voltage of ≈17.5 V, an output current of ≈0.522 μA, and a current density of ≈0.13 μA cm−2 under repeated finger tapping and can power a light‐emitting diode (LED) of 2 V practically. The study opens a new route for excellent flexible piezoelectric nanogenerators for promising application in an enormous arena of self‐powering portable and wearable electronic gadgets.
Electrodeposited Stable Binder‐Free Organic Ni(OH)2 Flexible Nanohybrid Electrodes for High‐Performance Supercapacitors
Authors: Singh Devraj , Jadhav Rohit G. , Das Apurba K.
Published: August 2019

Organic–inorganic hybrid materials with nanoscale morphologies gain significant attention as a potential candidate for energy storage applications. Herein, nickel hydroxide (Ni(OH)2) and benzo[2,1,3]selenadiazole (BSe)‐capped dipeptide amphiphiles are electrodeposited over flexible nickel foam (NF) substrates to fabricate organic–inorganic nanohybrids. The in situ electrochemical deposition of organic–inorganic nanohybrids is investigated by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, energy dispersive‐electron microscopy, and elemental mapping. The nanostructured morphology of the nanohybrid material is investigated by field‐emission scanning electron microscopy and transmission electron microscopy. The electrochemical performance and supercapacitor properties are examined in 1 m KOH aqueous solution. Aromatic diphenylalanine (FF)‐based nanohybrid BSeFF/Ni(OH)2 deposited on the NF electrode exhibit a specific capacitance of 1250 F g−1, whereas dileucine (LL)‐based nanohybrids BSeLL/Ni(OH)2 show a specific capacitance of 689 F g−1 at a current density of 2 A g−1.
Performance analysis of free space optical–based wireless sensor networks using corner cube retroreflectors
Authors: Althunibat Saud , Altarawneh Ziyad , Mesleh Raed
Published: August 2019

Asymmetric free space optical wireless sensor networks (FSO‐WSNs) have gained momentous attention lately due to the promise of minimal energy consumption at the distributed sensors along with eminent performance. Asymmetric FSO is accomplished using corner cube retroreflector (CCR) that is mounted on each sensor node. The CCR either reflects or absorbs the received laser beam from the fusion center to indicate its local decision regarding the monitored target. In this study, a bistatic channel is assumed where the transmitter and the receiver are located at different locations such that the double pass channel is modeled as a product of two independent turbulence channels. Novel performance analysis of the CCR‐based FSO‐WSN system in terms of the average bit error rate (BER) and the average decision error rate (DER) is presented. In particular, closed‐form expressions for the BER and the DER are derived using the Fox H‐function under different bistatic turbulent channel models including negative exponential, K‐turbulence, Gamma‐Gamma, and Malaga channel models. Monte Carlo simulation results are obtained to corroborate the accuracy of the derived analytical formulas where an exact match is reported over wide range of system and channel parameters. In addition, the influence of transmit power, distance, detection threshold, and turbulence parameters on the performance of the system is investigated and thoroughly discoursed.
EPB machine excavation of mixed soils – Laboratory characterisation
Authors: de Oliveira Daniela Garroux G. , Thewes Markus , Diederichs Mark S.
Published: August 2019

Earth pressure balance (EPB) tunnel boring machines are shield machines that rely on their own excavated material as a support medium to maintain the support pressure at the face. This material also needs to have the necessary properties to be extracted, transported and, finally, disposed of. Whenever the natural material does not fulfil the necessary requirements, additives like water, foam, polymers, and fines, must be added, modifying the excavated ground to the desired conditions. The rheological properties of any excavated material, together with any additives, must be investigated and understood, as they will influence the flow behaviour of this conditioned material, directly affecting the machine operation and tunnel logistics. While studies assessing the flowability related to the EPB excavation of sand or clay soils are available, there is a lack of information on mixed soils. This paper presents the results from a testing campaign with mixed clay‐sand samples, aiming to reproduce a simplified tropical weathered mixed soil, investigating its flow behaviour when changing certain controlled variables: clay‐sand proportions, clay mineral, size of the clastic grain mixed with clay, water content, and additives (foam and polymers). Results from the tests conducted with a flow table, a slump test, and a rheometer device were compared, providing insights about the flow behaviour of the tested samples and its interaction with an EPB machine.
Depression, quality of life, activities of daily living, and subjective memory after deep brain stimulation in Parkinson disease—A reliable change index analysis
Authors: Pusswald Gisela , Wiesbauer Patrick , Pirker Walter , Novak Klaus , Foki Thomas , Lehrner Johann
Published: August 2019

Objectives

In the field of Parkinson disease (PD) research, many studies have shown that deep brain stimulation (DBS) can soften side effects, which arise during long‐term medical therapy. This study focuses on the changes in depressive symptoms, quality of life (with the subdivisions physical and mental health), activities of daily living, and subjective memory functioning in PD patients testing the baseline and the outcome 1 year after DBS.

Methods

For the first time, the reliable change index (RCI) methodology was applied to compare PD‐DBS patients (n = 22) with best medically treated PD patients (PD‐BMT; n = 28), subjects with mild cognitive impairment (MCI, n = 43) and healthy controls (n = 25) in the above‐mentioned domains. The used questionnaires included the revised Beck Depression Inventory (BDI‐II), the Short Form (36) Health Survey (SF‐36), the Bayer Activities of Daily Living Scale (B‐ADL), and the Forgetfulness Assessment Inventory (FAI).

Results

The reliable change indices show high constant or improved results of the PD‐DBS patients in the domains subjective memory (85.7%‐100.0%), activities of daily living (60.0%‐90.0%), physical health summary (77.8%), depressive symptoms (61.9%), and mental health summary (50.0%) in comparison with the PD‐BMT, MCI, and control group.

Conclusions

DBS is an established alternative to best medical treatment of PD. The comparisons between the PD‐DBS and PD‐BMT groups do suggest that the domains mental health, depressive symptoms, and physical health benefit most, while the domains activities of daily living and subjective memory functioning are rather constant. Nevertheless, further research is needed to identify mechanisms and predictors that lead to improvement in individual cases.
Status of evidence‐based chronic diseases prevention implementation in Shanghai, China: A qualitative study
Authors: Shi Jianwei , Shi Leiyu , Geng Jinsong , Liu Rui , Gong Xin , Bo Xiaojie , Chen Ning , Liu Qian , Yang Yan , Wang Zhaoxin
Published: August 2019

Background

Given the rapid increase in chronic disease epidemics in developing countries and the lagging research and practice in evidence‐based chronic diseases prevention (EBCDP), we evaluated the status of public health practitioners' implementation of EBCDP and its impeding factors in China, as well as made a comparison between China and the developed countries to encourage better utilisation of this new field of science in China.

Methods

We interviewed health practitioners and patients from various health institutions in China and conducted a literature review to assess the current status of EBCDP practice in developed countries and identify the contextual driving factors.

Results

China is in its initial stage of EBCDP practice, as it lacks evidence‐based interventions. Moreover, health practitioners' awareness of EBCDP is inadequate. The lack of policy support, especially funding, has restricted the efficiency and quality of EBCDP in terms of its adoption, implementation, and maintenance. Currently, EBCDP practice is limited to the practitioners' spontaneous behaviours. The literature review showed that developed countries practising EBCDP did well in evidence development and awareness; however, much has yet to be explored regarding practitioners' adoption and implementation and the maintenance of evidence‐based practice. The impeding factors in developed countries were related to individual (patients and physicians) and organisational factors (such as resources, leaders, and climate).

Conclusion

To promote EBCDP practice in China, more evidence for effective chronic disease prevention programmes is needed, and multiple and flexible measures should be implemented for a successful transition to evidence‐based practice.
Risk factors for diabetic nephropathy complications in community patients with type 2 diabetes mellitus in Shanghai: Logistic regression and classification tree model analysis
Authors: Lou Jieqiong , Jing Limei , Yang Hui , Qin Fei , Long Wen , Shi Rong
Published: August 2019

Background

The prevalence of type 2 diabetes mellitus (T2DM) in China was 11.6% in 2010. Chronic complications are the main diabetes‐related cause of death and disability, accounting for more than 80% of the cost of diabetes treatment. Diabetic nephropathy (DN) is a common microvascular complication and is the second leading cause of end‐stage renal failure in China.

Objective

We aimed to analyse the DN status among community‐based T2DM patients and to explore risk factors for T2DM with DN.

Methods

This study was conducted in six communities of Shanghai. We administered a questionnaire, physical examination, and biochemical tests to 5078 patients with T2DM. Logistic regression and the classification tree model were used to analyse risk factors for T2DM with DN.

Results

In total, 1937 patients were diagnosed with DN (prevalence 38.4%). The logistic regression model indicated that course of disease more than 15 years, body mass index (BMI) greater than 24 kg/m2, haemoglobin A1c (HbA1c) greater than 7.5%, fasting blood glucose (FBG) greater than 11.0 mmol/L, total cholesterol (TC), and high‐density lipoprotein (HDL)‐C control failure, hypertension, and diabetic retinopathy were risk factors for T2DM with DN (P < .05). The classification tree model identified seven risk factors (HbA1c, FBG, hypertension, postprandial blood glucose, BMI, triacylglycerol, and HDL), of which, HbA1c (cut‐off point 7.45%), hypertension, and FBG showed the strongest association.

Conclusion

This suggests that screening for DN based on HbA1c, FBG, and hypertension should be more extensively promoted by the government on a community level, more attention should be focused on patients' health management, and that patients should be educated on self‐management.
Preventable incidence of carcinoma associated with adiposity, alcohol and physical inactivity according to smoking status in the United States
Authors: Song Mingyang , Giovannucci Edward
Published: August 2019

The changing profile of lifestyles and their intricate relationships with smoking indicate the importance of accounting for smoking status when assessing cancer preventability. We assessed the association of body mass index, weight change, alcohol intake and physical activity with risk of total carcinoma among 53,195 smokers and 62,842 nonsmokers in two prospective cohorts. Then, leveraging the national prevalence estimates, we calculated the population attributable risk (PAR) for healthy lifestyle defined as body mass index ≥18.5 and <27.5 kg/m2, mid‐life weight change of ≤20 pounds, no or moderate alcohol drinking (≤1 and 2 drinks/day for women and men, respectively) and weekly moderate or vigorous physical activity of at least 150 min. The PAR (95% CI) for healthy lifestyle was 18% (14–22%) in nonsmokers and 14% (10–19%) in smokers among women, and 20% (12–27%) in nonsmokers and 11% (5–17%) in smokers among men. While adiposity accounted for a substantially higher proportion of carcinoma cases in nonsmokers than smokers (16% vs. 2% in women, 15% vs. 2% in men), alcohol contributed more in smokers than nonsmokers (7% vs. 3% in women, 8% vs. 1% in men). When more strict criteria were used to define healthy lifestyle, the PAR estimates further increased (for women: 37% in smokers and 32% in nonsmokers; for men: 15% and 24%, respectively). In conclusion, lifestyle modification has great potential to reduce cancer risk in both smokers and nonsmokers. Weight control and reducing alcohol consumption should be prioritized for cancer prevention in nonsmokers and smokers, respectively.