bluuebunny/crossref_metadata_2025 huggingface dataset:
Chlorbenzol [MAK Value Documentation in German language, 2018]
Authors: Hartwig A. ,   MAK Commission
Published: July 2018

The German Commission for the Investigation of Health Hazards of Chemical Compounds in the Work Area has re‐evaluated chlorobenzene [
108‐90‐7
] to derive a maximum concentration at the workplace (MAK value), considering all toxicity endpoints. Adverse effects are a depression of the central nervous system in humans and histological alterations in liver and kidneys in rats. A 2‐generation reproduction study with chlorobenzene vapour in Sprague‐Dawley rats resulted in a NOAEC of 50 ml/m
3
. Based on this NOAEC, a MAK value of 5 ml/m
3
is derived. This value is supported by a study with healthy volunteers at rest, who showed no neurotoxic or chemosensory effects at a NAEC of 5.9 ml/m
3
, which takes the increased respiratory volume at the work place into account. As systemic effects are critical, the substance remains assigned to Peak Limitation Category II and the excursion factor of 2 is confirmed. Chlorobenzene caused a statistically significantly increased incidence of neoplastic nodules in the liver of male F344 rats in a carcinogenicity study at the highest dose of 120 mg/kg body weight and day. As chlorobenzene is genotoxic only at high doses given intraperitoneally, and female rats and mice did not show any tumours in this study, it remains regarded neither as a carcinogen nor as a germ cell mutagen. From a synopsis of all data, the classification of chlorobenzene in Pregnancy Risk Group C is maintained. Chlorobenzene did not lead to contact sensitization in mice and guinea pigs.
Oleylsarkosin [MAK Value Documentation in German language, 2018]
Authors: Hartwig A. ,   MAK Commission
Published: July 2018

The German Commission for the Investigation of Health Hazards of Chemical Compounds in the Work Area has re‐evaluated the maximum concentration at the workplace (MAK value) of oleoyl sarcosine [
110‐25‐8
].

Critical effects are lung fibrosis and inflammation at the epiglottis in rats in a 28‐day study at an aerosol concentration of 6 mg/m
3
, the lowest concentration tested. A BMDL
05
of 1.3 mg/m
3
as surrogate for a NOAEC for fibrosis had been calculated. For inflammation at the epiglottis an NAEC of 2 mg/m
3
was estimated. Taken together, a MAK value of 0.1 mg/m
3
had been set. Since the NAEC for inflammation at the epiglottis is similar to the BMDL
05
for lung toxicity, the MAK value had been established for the inhalable fraction (I). The MAK value is now lowered to 0.05 mg/m
3
(I) considering the increased respiratory volume at the workplace (see List of MAK and BAT Values, chapters I b and I c).

Oleoyl sarcosine remains assigned to Peak Limitation Category II because the fibrosis is considered not to result from an immediate irritation. As the half‐life in the lung is not known, the default excursion factor of 2 is retained.

There are still no data on sensitization of the airways, no clinical evidence and only an equivocal result from a maximization test for skin sensitization.
Acrylic acid ethyl ester [MAK Value Documentation, 2016]
Authors: Hartwig A. ,   MAK Commission
Published: July 2018

The German Commission for the Investigation of Health Hazards of Chemical Compounds in the Work Area has re‐evaluated the maximum concentration at the workplace (MAK value) of ethyl acrylate [
140‐88‐5
] of 5 ml/m
3
, considering all toxicity endpoints. Available unpublished study reports and publications are described in detail. The critical effect of ethyl acrylate is irritation of eye and nose in humans and the olfactory mucosa in rats and mice. The chronic NOAEC in rats is 5 ml/m
3
. Since 2014 the Commission uses an empirical approach to set MAK values for substances with critical effects on the upper respiratory tract or the eyes. Accordingly, the MAK value has to be lowered to 2 ml/m
3
, which is confirmed in a recent volunteer study with a NOAEC of 2.5 and a LOAEC of 5 ml ethyl acrylate/m
3
. As local effects are critical, the assignment to Peak Limitation Category I and the excursion factor of 2 are confirmed. Developmental toxicity studies with ethyl acrylate show no risk for the embryo or foetus if the MAK value is observed, and the assignment to Pregnancy Risk Group C is retained. Ethyl acrylate is not genotoxic in vivo and not carcinogenic. Skin contact may contribute significantly to systemic toxicity and ethyl acrylate is designated with an “H” notation. The available data confirm that the substance is a skin sensitizer and the designation with “Sh” is retained. There are no data concerning the potential for respiratory sensitization.
tert‐Butylacetat [MAK Value Documentation in German language, 2018]
Authors: Hartwig A. ,   MAK Commission
Published: July 2018

The German Commission for the Investigation of Health Hazards of Chemical Compounds in the Work Area has re‐evaluated the maximum concentration at the workplace (MAK value) and the Pregnancy Risk Group for
tert
‐butyl acetate [
540‐88‐5
].

Critical effects are transient acute neurotoxic symptoms which are observed in a 90‐day‐study with mice with a NOAEC of 100 ml/m
3
. From this concentration the former MAK value of 50 ml/m
3
was derived. It is now lowered to 20 ml/m
3
taking into account the increased respiratory volume at the workplace because the blood:air partition coefficient of
tert
‐butyl acetate is > 5 (see List of MAK and BAT Values, chapters I b and I c). This value also provides protection from irritation. Since a systemic effect is critical, Peak Limitation Category II is retained. The excursion factor of 2 is set in spite of the short half‐life of
tert
‐butyl acetate in blood as it is an acute effect for which an adaptation during subchronic exposure has been noticed. Therefore, peaks of exposure will not enhance the effect at chronic exposure. Furthermore, since the incidences after 90 days at 400 ml/m
3
are low, the true NAEC might have been higher than 100 ml/m
3
.

tert
‐Butyl acetate had been classified in Pregnancy Risk Group C because the NOAEC for fetotoxicity is 1600 ml/m
3
in a screening study in rats and taking into consideration the data for the metabolite
tert
‐butyl alcohol. There is no new data on developmental toxicity. This classification is retained even considering the increased respiratory volume at the workplace.
Finite‐time synchronization and adaptive synchronization of memristive recurrent neural networks with delays
Authors: Li Xiaofan , Fang Jian‐an , Li Huiyuan
Published: July 2018

This paper solves the finite‐time synchronization and adaptive synchronization problems of drive‐response memristive recurrent neural networks with delays under two control methods. First, the state‐feedback control rule containing delays and the adaptive control rule are designed for realizing synchronization of drive‐response memristive recurrent neural networks in finite time. Then, on the basis of the Lyapunov stability theory, many algebraic sufficient conditions are obtained to guarantee finite‐time synchronization and adaptive synchronization of drive‐response memristive recurrent neural networks via two control methods, which are easily verified. In addition, the estimation of the upper bounds of the settling time of finite‐time synchronization is obtained. Lastly, to illustrate the effectiveness of the obtained theoretical results, two examples are given.
Simultaneous Enhancement in Electrical Conductivity and Thermopower of n‐Type NiETT/PVDF Composite Films by Annealing
Authors: Wolfe Rylan M. W. , Menon Akanksha K. , Fletcher Thomas R. , Marder Seth R. , Reynolds John R. , Yee Shannon K.
Published: July 2018

Nickel ethenetetrathiolate (NiETT) polymers are promising n‐type thermoelectric (TE) materials, but their insolubility requires the use of an inert polymer matrix to form films, which is detrimental to the TE performance. In this work, the use of thermal annealing as a post‐treatment process simultaneously enhances the electrical conductivity from 6 ± 2 to 23 ± 3 S cm−1 and thermopower from −28 ± 3 to −74 ± 4 µV K−1 for NiETT/PVDF composite films. Spectroscopic characterization reveals that the underlying mechanism involves removal of residual solvent and volatile impurities (carbonyl sulfide and water) in the NiETT polymer backbone. Additionally, microscopic characterization reveals morphological changes caused by a densification of the film that improves chain packing. These effects result in a 25 × improvement in power factor from 0.5 to 12.5 µW m−1 K−2 for NiETT/PVDF films and provide insight into the composition of these coordination polymers that maintain their stability under ambient conditions.
Citrate‐Based Fluorescent Biomaterials
Authors: Shan Dingying , Hsieh Jer‐Tsong , Bai Xiaochun , Yang Jian
Published: July 2018

Fluorescence imaging has emerged as a promising technique for monitoring and assessing various biologically relevant species in cells and organisms, driving the demand for effective fluorescent agents with good biocompatibility and high fluorescence performance. However, traditional fluorescent agents, such as quantum dots (QDs) and organic dyes, either suffer from toxicity concerns or poor fluorescence performance (e.g., low photobleaching‐resistance). In this regard, citrate‐based fluorescent biomaterials, which are synthesized from the natural and biocompatible precursor of citric acid (CA), have become competitive alternatives for fluorescence imaging owing to their biocompatibility, cost effectiveness, straightforward synthetic routes, flexible designability, as well as strong fluorescence with adjustable excitation/emission wavelengths. Accordingly, numerous citrate‐based biomaterials, including carbon dots (CDs), biodegradable photoluminescent polymers (BPLPs), and small molecular fluorophores, have been developed and researched in the past few decades. This review discusses recent progress in the research and development of citrate‐based fluorescent materials with emphasis on their design and synthesis considerations, material properties, fluorescence properties and mechanisms, as well as biomedical applications. It is expected that this review will provide an insightful discussion on the citrate‐based fluorescent biomaterials, and lead to innovations for the next generation of fluorescent biomaterials and fluorescence‐based biomedical technology.
Halogenated Aza‐BODIPY for Imaging‐Guided Synergistic Photodynamic and Photothermal Tumor Therapy
Authors: Zhao Menglong , Xu Yunjian , Xie Mingjuan , Zou Liang , Wang Zhaoli , Liu Shujuan , Zhao Qiang
Published: July 2018

It is always a huge challenge to develop novel near‐infrared (NIR) phototherapeutic agents suitable for imaging‐guided cancer therapy. In order to clarify the positive heavy atom effects on the photodynamic and photothermal efficiencies of phototherapeutic agents, a series of chlorine‐, bromide‐, or iodine‐substituted aza‐BODIPYs (B2, B3, and B4, respectively) are designed and synthesized. Among them, B4 exhibits both excellent photodynamic and photothermal effects (singlet oxygen yield of B4 is 1.57 times more than that of B3) and excellent photothermal effects (1.3 °C higher than that of B3). Then, nanoparticles of B4 (IABNs) with excellent biocompatibility are prepared by coating hydrophobic B4 with hydrophilic polymer DSPE‐mPEG5000. IABN exhibits high photostability, excellent biocompatibility, and low dark toxicity both in vivo and in vitro. Furthermore, IABN shows the enhanced photodynamic effect and high photothermal conversion efficiency (34.8%). In addition, the strong fluorescence emission of IABN makes it suitable for fluorescence imaging‐guided tumor therapy in vivo. Finally, IABN has successfully healed the Hela tumor‐bearing mice under NIR fluorescence imaging‐ and photothermal imaging‐guided synergistic photothermal and photodynamic therapy with low side effects, demonstrating that it is promising for future clinical applications.
Challenges for Developing Rechargeable Room‐Temperature Sodium Oxygen Batteries
Authors: Sun Bing , Pompe Constantin , Dongmo Saustin , Zhang Jinqiang , Kretschmer Katja , Schröder Daniel , Janek Jürgen , Wang Guoxiu
Published: July 2018

The development of high energy‐density and low‐cost energy storage devices requires new chemistry beyond the horizon of current state‐of‐the‐art lithium‐ion batteries. Recently, sodium/oxygen (Na/O2) batteries have attracted great attention as one possible battery type among the new generation of rechargeable batteries. They convince with superior energy density, a relatively simple cell reaction, and abundance of sodium. Research on Na/O2 batteries has progressed quickly in recent years. However, a fundamental understanding underpinning the complex chemical/electrochemical side reactions is still insufficient, and many challenges remain unsolved for real practical applications. Herein, recent achievements and remaining issues for the development of rechargeable Na/O2 batteries are summarized. The discussion focuses on cell reaction mechanisms as well as cathode materials, sodium anodes, and electrolytes as key components of this type of battery. Furthermore, perspectives for future research and technological advances of Na/O2 batteries are outlined.
Gyroid “srs” Networks: Photonic Materials Beyond Nature
Authors: Goi Elena , Cumming Benjamin P. , Gu Min
Published: July 2018

The gyroid “srs” network is a bio‐inspired, 3D periodic network with both cubic symmetry and chirality, which is modeled (and named) after the SrSi2 crystal. It is an excellent starting point for the development of chiral photonic materials and a powerful platform for the study of complex morphologies and novel photonic topological states. In this Progress Report, the most advanced top‐down fabrication techniques, characterization methods, and applications of metallic and dielectric gyroid micro and nanostructures are reviewed. More importantly, new research directions involving these bio‐inspired photonic materials are presented and their potential applications in integrated photonics, topological photonics, and medical sciences are discussed.
Small‐Molecule Emitters with High Quantum Efficiency: Mechanisms, Structures, and Applications in OLED Devices
Authors: Wei Qiang , Fei Nannan , Islam Amjad , Lei Tao , Hong Ling , Peng Ruixiang , Fan Xi , Chen Liang , Gao Pingqi , Ge Ziyi
Published: July 2018

Organic emitters play a vital role in determining the overall performance of organic light emitting diode (OLED) devices. Traditional fluorescent emitters can only achieve external quantum efficiency (EQE) of 5%, far below expectation; therefore many efforts have been spent on increasing the EQE of OLEDs. Phosphorescence, thermally activated delayed fluorescence, triplet–triplet annihilation, and hybridized local and charge transfer are the most widely applied approaches to harvest the 75% triplet excitons for luminescence. As for selecting or designing suitable emitters for practical applications, it is strongly demanded to have an overall view about emitters of high exciton utilizing efficiency (EUE) from molecule level, i.e., the four common approaches mentioned above and some latest ones of the doublet, singlet fission, triplet–polar annihilation, and rotationally accessed spin state inversion, and also from the aggregated state such as aggregation‐induced emission. In this review, the current progress of highly efficient emitters is presented, covering the chemical structures, the high‐EUE mechanisms in molecule level and aggregated state, and their applications in OLED devices. This review hopefully will illustrate highly efficient electroluminescent materials and their mechanisms, but more importantly, provide helpful information on how to design or select suitable emitters for specific OLED devices.
Visible‐Light‐Promoted Redox‐Neutral Cyclopropanation Reactions of α‐Substituted Vinylphosphonates and Other Michael Acceptors with Chloromethyl Silicate as Methylene Transfer Reagent
Authors: Guo Ting , Zhang Li , Liu Xiaobo , Fang Yewen , Jin Xiaoping , Yang Yi , Li Yan , Chen Bin , Ouyang Minghui
Published: July 2018

The alkene cyclopropanation with chloromethyl silicate as a methylene transfer reagent has been accomplished via visible‐light‐mediated redox‐neutral catalysis. This method features broad functional group tolerance and mild conditions. In addition to α‐substituted vinylphosphonates, a range of Michael acceptors including α,β‐unsaturated acrylate, ketone, amide and sulfone are suitable substrates for this photocatalytic cyclopropanation. An application of this protocol to the cyclopropanation of estrone derivative is also presented.

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Ultra‐Lightweight 3D Carbon Current Collectors: Constructing All‐Carbon Electrodes for Stable and High Energy Density Dual‐Ion Batteries
Authors: Zhou Zhili , Li Na , Yang Yazheng , Chen Haosen , Jiao Shuqiang , Song Wei‐Li , Fang Daining
Published: July 2018

Dual‐ion batteries (DIBs) attract great interest because they allow two types of ions for reversibly intercalating into electrodes, resulting in various advantages. However, there are three critical problems using graphite‐based cathodes, namely, low active material proportion in the electrodes, current collector corrosion, and massive cathode variation. For addressing these problems, an ultra‐lightweight 3D carbon current collector (CCC) is developed to fabricate all‐carbon electrodes as both cathodes and anodes. Compared with the conventional DIBs using Al and Cu foils as current collectors, the DIBs with 3D CCC of electrically conductive pathways and sufficient ionic diffusion channels deliver enhanced specific capacity stabilized around 140 and 120 mAh g−1 at 0.5 and 1C, respectively. The electrochemically inert 3D CCC could essentially promote the energy density when calculating the entire electrode mass, along with long‐life cycle stability of 1000 cycles at 5C and no electrochemical corrosion on either anodes or cathodes. With an in situ optical microscope, the cathode expansion is found to massively reduce because the porous 3D CCC could effectively alleviate the huge volume. The results suggest a novel strategy for achieving low‐cost and high energy density DIBs with both mechanically and electrochemically stable features.
Theoretical Investigation of 2D Conductive Microporous Coordination Polymers as Li–S Battery Cathode with Ultrahigh Energy Density
Authors: Gao Guoping , Zheng Fan , Pan Feng , Wang Lin‐Wang
Published: July 2018

Even though tremendous achievement has been made experimentally in the performance of lithium–sulfur (Li–S) battery, theoretical studies in this area are lagging behind due to the complexity of the Li–S systems and the effects of solvent. For this purpose, a new methodology is developed for investigating the 2D hexaaminobenzene‐based coordination polymers (2D‐HAB‐CPs) as cathode candidate materials for Li–S batteries via density functional theory calculations in combination with an in‐house developed charge polarized solvent model and a genetic algorithm structure global search code. With high ratios of transition metal atoms and two‐coordinated nitrogen atoms, excellent electric conductivity, and structural porosity, the 2D‐HAB‐CP is able to address all of the three main challenges facing Li–S batteries: confining the lithium polysulfides from dissolution, facilitating the electron conductivity and buffering the volumetric expansion during the lithiation process. In addition, the theoretical energy density of this system is as high as 1395 Wh kg−1. These results demonstrate that the 2D‐HAB‐CP is a promising cathode material for Li–S batteries. The proposed computational framework not only opens a new avenue for understanding the key role played by solution and liquid electrolytes in Li–S batteries, but also can be generally applied to other processes with liquids involved.
Surgical management of carcinoma in situ at ductal resection margins in patients with extrahepatic cholangiocarcinoma
Authors: Wakai Toshifumi , Sakata Jun , Katada Tomohiro , Hirose Yuki , Soma Daiki , Prasoon Pankaj , Miura Kohei , Kobayashi Takashi
Published: July 2018

Recent advances in dimensional imaging, surgical technique, and perioperative patient care have resulted in increased rates of complete resection with histopathologically negative margins and improved surgical outcomes in patients with extrahepatic cholangiocarcinoma. However, achieving cancer‐free resection margins at ductal stumps in surgery for this disease remains challenging because of longitudinal extension, which is one of the hallmarks of extrahepatic cholangiocarcinoma. When the ductal resection margins are shown to be positive on examination of frozen sections, discrimination between carcinoma in situ and invasive carcinoma is clinically important because residual carcinoma in situ may lead to late local recurrence whereas residual invasive carcinoma is associated with early local recurrence. Residual invasive carcinoma at the ductal margins should be avoided whenever technically feasible. Residual “carcinoma in situ” at the ductal margins appears to be allowed in resection for the advanced disease because it has less effect on survival than other adverse prognostic factors (pN1 and/ or pM1). However, in surgery for early‐stage (pTis‐2N0M0) extrahepatic cholangiocarcinoma, residual carcinoma in situ at the ductal margins may have an adverse effect on long‐term survival, so should be avoided whenever possible. In this review, we focus on the histopathological term “carcinoma in situ,” the biological behavior of residual carcinoma in situ at ductal resection margins, intraoperative histological examination of the ductal resection margins, outcome of additional resection for positive ductal margins, and adjuvant therapy for patients with positive margins.
Phosphine‐Catalyzed Reactions with Unsaturated Carbonyl Compounds
Authors: Nallapati Suresh Babu , Chuang Shih‐Ching
Published: July 2018

Organophosphines are versatile Lewis basic catalysts that have been confirmed as powerful tools in organic synthesis for the past two decades. The nucleophilic addition of organophosphines to electron‐deficient species can be divided into two categories: phosphine‐catalyzed and stoichiometric phosphine‐mediated transformations. In this focus review, we summarize recent examples of phosphine‐catalyzed addition and annulation reactions with allenoates and alkynoates. In addition, we discuss our recent efforts in the development of unusual phosphine‐mediated α‐addition reactions with enynedioates, enynoates, and oligoynoates and its application in novel functional fullerene derivatives as n‐type materials in organic photovoltaics.
Base‐Promoted Synthesis of β‐Ketophosphine Oxides from Diphenylphosphorylallenes
Authors: Ruan Li‐Heng , Wang Qiang , Sun Jing , Zhou Ming‐Dong
Published: July 2018

The transition‐metal‐free synthesis of β‐ketophosphine oxides from diphenylphosphorylallenes in the presence of pyrrolidine and silica gel has been developed under mild reaction conditions. This simple and efficient transformation tolerates a wide range of diphenylphosphorylallenes with different functional groups, and affords the desired products in moderate to excellent yields.
Fluorination of Alkylidenecyclopropanes
Authors: Zhang Xiao‐Yu , Li Peng‐Hua , Shi Min
Published: July 2018

Introducing fluorine or fluorine‐containing groups into organic compounds or biologically active compounds to improve their physical and chemical properties such as membrane permeability, bioavailability and metabolic stability has attracted intensive attention in synthetic chemistry. During the last decades, relying on the high reactivity of alkylidenecyclopropanes (ACPs), many interesting synthetic methods have been developed to prepare the corresponding fluorinated organic compounds and the related scaffolds by our group and others. This review article summarized the recent advances in the fluorination of alkylidenecyclopropanes and classified the fluorinations into monofluorination, difluoromethylation, trifluoromethylation and trifluoromethylthiolation reactions.
Sporadic Fatal Insomnia in Europe: Phenotypic Features and Diagnostic Challenges
Authors: Abu‐Rumeileh Samir , Redaelli Veronica , Baiardi Simone , Mackenzie Graeme , Windl Otto , Ritchie Diane L. , Didato Giuseppe , Hernandez‐Vara Jorge , Rossi Marcello , Capellari Sabina , Imperiale Daniele , Rizzone Mario Giorgio , Belotti Alessia , Sorbi Sandro , Rozemuller Annemieke J. M. , Cortelli Pietro , Gelpi Ellen , Will Robert G. , Zerr Inga , Giaccone Giorgio , Parchi Piero
Published: July 2018

Objective

Comprehensively describe the phenotypic spectrum of sporadic fatal insomnia (sFI) to facilitate diagnosis and management of this rare and peculiar prion disorder.

Methods

A survey among major prion disease reference centers in Europe identified 13 patients diagnosed with sFI in the past 20 years. We undertook a detailed analysis of clinical and histopathological features and the results of diagnostic investigations.

Results

Mean age at onset was 43 years, and mean disease duration 30 months. Early clinical findings included psychiatric, sleep, and oculomotor disturbances, followed by cognitive decline and postural instability. In all tested patients, video‐polysomnography demonstrated a severe reduction of total sleep time and/or a disorganized sleep. Cerebrospinal fluid (CSF) levels of proteins 14‐3‐3 and t‐tau were unrevealing, the concentration of neurofilament light protein (NfL) was more consistently increased, and the real‐time quaking‐induced conversion assay (RT‐QuIC) revealed a positive prion seeding activity in 60% of cases. Electroencephalography and magnetic resonance imaging showed nonspecific findings, whereas fluorodeoxyglucose positron emission tomography (FDG‐PET) demonstrated a profound bilateral thalamic hypometabolism in 71% of cases. Molecular analyses revealed PrPSc type 2 and methionine homozygosity at PRNP codon 129 in all cases.

Interpretation

sFI is a disease of young or middle‐aged adults, which is difficult to reconcile with the hypothesis of a spontaneous etiology related to stochastic, age‐related PrP misfolding. The combination of psychiatric and/or sleep‐related symptoms with oculomotor abnormalities represents an early peculiar clinical feature of sFI to be valued in the differential diagnosis. Video‐polysomnography, FDG‐PET, and especially CSF prion RT‐QuIC and NfL constitute the most promising supportive diagnostic tests in vivo. Ann Neurol 2018;84:347–360
Catalytic Transformations of Alkynes into either α‐Alkoxy or α‐Aryl Enolates: Mannich Reactions by Cooperative Catalysis and Evidence for Nucleophile‐Directed Chemoselectivity
Authors: Sahani Rajkumar Lalji , Patil Manoj D. , Wagh Sachin Bhausaheb , Liu Rai‐Shung
Published: July 2018

The catalytic formation of gold enolates from alkynes, nitrones, and nucleophiles is described, and their Mannich reactions result in nucleophile‐directed chemoselectivity through cooperative catalysis. For 1‐alkyn‐4‐ols and 2‐ethynylphenols, their gold‐catalyzed nitrone oxidations afforded N‐containing dihydrofuran‐3(2H)‐ones with syn selectivity. The mechanism involves the Mannich reactions of gold enolates with imines through an O‐H‐N hydrogen‐bonding motif. For aryloxyethynes, their gold enolates react selectively with nitrones to deliver 3‐alkylidenebenzofuran‐2‐ones, as controlled by a C‐H‐O hydrogen‐bonding motif.
Multidirectional Activity Control of Cellular Processes by a Versatile Chemo‐optogenetic Approach
Authors: Chen Xi , Venkatachalapathy Muthukumaran , Dehmelt Leif , Wu Yao‐Wen
Published: July 2018

The spatiotemporal dynamics of proteins or organelles plays a vital role in controlling diverse cellular processes. However, acute control of activity at distinct locations within a cell is challenging. A versatile multidirectional activity control (MAC) approach is presented, which employs a photoactivatable system that may be dimerized upon chemical inducement. The system comprises second‐generation SLF*‐TMP (S*T) and photocaged NvocTMP‐Cl dimerizers; where, SLF*‐TMP features a synthetic ligand of the FKBP(F36V) binding protein, Nvoc is a caging group, and TMP is the antibiotic trimethoprim. Two MAC strategies are demonstrated to spatiotemporally control cellular signaling and intracellular cargo transport. The novel platform enables tunable, reversible, and rapid control of activity at multiple compartments in living cells.
Rhenium Metal and Rhenium Nitride Thin Films Grown by Atomic Layer Deposition
Authors: Hämäläinen Jani , Mizohata Kenichiro , Meinander Kristoffer , Mattinen Miika , Vehkamäki Marko , Räisänen Jyrki , Ritala Mikko , Leskelä Markku
Published: July 2018

Rhenium is both a refractory metal and a noble metal that has attractive properties for various applications. Still, synthesis and applications of rhenium thin films have been limited. We introduce herein the growth of both rhenium metal and rhenium nitride thin films by the technologically important atomic layer deposition (ALD) method over a wide deposition temperature range using fast, simple, and robust surface reactions between rhenium pentachloride and ammonia. Films are grown and characterized for compositions, surface morphologies and roughnesses, crystallinities, and resistivities. Conductive rhenium subnitride films of tunable composition are obtained at deposition temperatures between 275 and 375 °C, whereas pure rhenium metal films grow at 400 °C and above. Even a just 3 nm thick rhenium film is continuous and has a low resistivity of about 90 μΩ cm showing potential for applications for which also other noble metals and refractory metals have been considered.
A Click Cage: Organelle‐Specific Uncaging of Lipid Messengers
Authors: Wagner Nicolai , Stephan Milena , Höglinger Doris , Nadler André
Published: July 2018

Lipid messengers exert their function on short time scales at distinct subcellular locations, yet most experimental approaches for perturbing their levels trigger cell‐wide concentration changes. Herein, we report on a coumarin‐based photocaging group that can be modified with organelle‐targeting moieties by click chemistry and thus enables photorelease of lipid messengers in distinct organelles. We show that caged arachidonic acid and sphingosine derivatives can be selectively delivered to mitochondria, the ER, lysosomes, and the plasma membrane. By comparing the cellular calcium transients induced by localized uncaging of arachidonic acid and sphingosine, we show that the precise intracellular localization of the released second messenger is crucial for the signaling outcome. Ultimately, we anticipate that this new class of caged compounds will greatly facilitate the study of cellular processes on the organelle level.
The role of introduced species in the decline of a highly endemic fish fauna in Central Mexico
Authors: Gesundheit Pablo , Macías Garcia Constantino
Published: July 2018

Central Mexico, home to a unique and imperilled freshwater fish fauna, high in endemism, is also a very densely populated region with considerable human activity.

Aquatic systems in the region have been heavily disturbed by human activity in the form of species introductions, pollution, and habitat modification, which has resulted in the extirpation of native fishes and the alteration of the native fish fauna.

An analysis of the roles of these factors in the decline of the fish fauna and an overview of its conservation status are presented. Both current and historic fish assemblages were characterized and water physicochemical parameters recorded at 62 localities within the region. Water quality, hydrological modification, and the presence of introduced species were used as variables in a linear model to explore their respective influence on the integrity of local fish assemblages.

Analyses suggest that both water quality and the presence of introduced species have had adverse impacts of similar magnitude on the conservation status of native species, whereas hydrological modification has had no statistically significant effect.

This survey revealed the profound alteration of the fish fauna. Only 40% of the expected native populations were found, and only 30% of the sampled assemblages were free of introduced species. As little as 17% of the sampled assemblages were taxonomically intact. The mean species richness per locality was only half of that indicated by historical records. The conservation value of springs, where many threatened microendemics can still be found, is highlighted, and we argue that their small size and isolation make them key targets for conservation efforts.
Synthesis and antitumor evaluation of novel 4‐anilino‐7,8‐dihydropyrido[4,3‐d]pyrimidine‐6(5H)‐carboxylate derivatives as potential EGFR inhibitors
Authors: Zhang Dajun , Yan Yan , Jin Ge , Liu Bo , Ma Xiaoliang , Han Dan , Jia Xiaojian
Published: July 2018

Novel series of 4‐anilino‐7,8‐dihydropyrido[4,3‐d]pyrimidine‐6(5H)‐carboxylates (5a–p, 7, and 8a–e) were synthesized and evaluated for their antiproliferative activity against the A549, HT29, H460, and H1975 cancer cell lines in vitro. Nine compounds (5a–c, 5i, 5j, 7, 8a, 8b, 8i) demonstrated moderate to significant cytotoxic activity with IC50 values below 18 µM on A549 cells, which were comparable to that of the reference gefitinib (IC50 = 18.44 µM). Especially, the further enzymatic analysis on epidermal growth factor receptor (EGFR), HER2, and VEGFR identified compound 5a as a promising hit that exhibited considerable potency both in cellular (IC50 = 5.67, 17.04, 11.29, and 12.65 µM, respectively) and EGFR enzymatic assays (IC50 = 14.8 nM). Compound 5a was capable of down‐regulating the expression of EGFR and inhibited EGFR phosphorylation in a dose‐dependent manner, representing a potential EGFR candidate for further optimization.
An Amplitude‐ and Rate‐Saturated Controller for Linear Plants
Authors: Baiomy Nehal , Kikuuwe Ryo
Published: July 2018

This paper proposes a new nonlinear controller applicable to single‐input linear systems under bounded disturbance. The controller provides control signals satisfying specified amplitude and rate‐of‐change limitations. This feature is realized by its sliding mode‐like structure comprising a set‐valued function. The controller also employs a state‐dependent parameter to broaden the region of attraction and to shrink the terminal attractor. In addition, this paper provides a discrete‐time implementation of the proposed controller based on a model‐based implicit discretization scheme. Numerical examples show the validity of the proposed controller.
Observer‐Based Adaptive Output Feedback Fault Tolerant Control for Nonlinear Hydro‐Turbine Governing System with State Delay
Authors: Yi Yapeng , Chen Diyi , Li Huanhuan , Li Chaoshun , Zhou Jianzhong
Published: July 2018

This paper focuses on the problem of adaptive output feedback fault tolerant control for a nonlinear hydro‐turbine governing system. A dynamic mathematical model of the system is established, which aims to investigate the dynamic performance of the model under servomotor delay and actuator faults. Then, a fault estimation adaptive observer is proposed to achieve online real‐time diagnosis of system faults. Based on the online fault estimation information, an observer‐based adaptive output feedback fault tolerant controller is designed. Furthermore, under reasonable assumptions, the results demonstrate that the closed‐loop control system can achieve global asymptotic stability by Lyapunov function. Finally, the numerical simulation results are presented to indicate the satisfaction control effectiveness of the proposed scheme.
A sensitive resonance Rayleigh light scattering method for alpinetin using gold nanorods probes
Authors: Bi Shuyun , Sun Xiaoyue , Wang Yu , Wu Jun , Zhou Huifeng
Published: July 2018

A sensitive resonance Rayleigh light scattering (RLS) assay for alpinetin was developed based on alpinetin‐modified gold nanorods (AuNRs). Alpinetin could interact with AuNRs and formed a new assembly by electrostatic attraction. In pH 7.4 Tris–HCl buffer solution, the assembly of alpinetin–AuNRs showed a sensitive RLS signal. Under optimum conditions, the magnitude of enhanced RLS intensity (ΔIRLS) was proportional to the concentration of alpinetin over the range 0.027–3.24 μg ml−1, with a detection limit of 1.79 ng ml−1 (by 3σ). The developed RLS method was successfully applied to the detection of alpinetin in real or synthesized samples. Alpinetin recoveries were 90.4–108.7% with an RSD of 0.82–2.9% (n = 5) for Alpinia katsumadai samples, and 95.1–103.7% with an RSD of 0.28–3.9% (n = 5) for synthesized samples. The results showed that this new approach was convenient, reliable and sensitive.
Altered resting‐state functional connectivity of the putamen and internal globus pallidus is related to speech impairment in Parkinson's disease
Authors: Manes Jordan L. , Tjaden Kris , Parrish Todd , Simuni Tanya , Roberts Angela , Greenlee Jeremy D. , Corcos Daniel M. , Kurani Ajay S.
Published: July 2018

Introduction

Speech impairment in Parkinson's disease (PD) is pervasive, with life‐impacting consequences. Yet, little is known about how functional connections between the basal ganglia and cortex relate to PD speech impairment (PDSI). Whole‐brain resting‐state connectivity analyses of basal ganglia nuclei can expand the understanding of PDSI pathophysiology.

Methods

Resting‐state data from 89 right‐handed subjects were downloaded from the Parkinson's Progression Markers Initiative database. Subjects included 12 older healthy controls (“OHC”), 42 PD patients without speech impairment (“PDN”), and 35 PD subjects with speech impairment (“PDSI”). Subjects were assigned to PDN and PDSI groups based on the Movement Disorders Society Unified Parkinson's Disease Rating Scale (MDS‐UPDRS) Part III speech item scores (“0” vs. “1–4”). Whole‐brain functional connectivity was calculated for four basal ganglia seeds in each hemisphere: putamen, caudate, external globus pallidus (GPe), and internal globus pallidus (GPi). For each seed region, group‐averaged connectivity maps were compared among OHC, PDN, and PDSI groups using a multivariate ANCOVA controlling for the effects of age and sex. Subsequent planned pairwise t‐tests were performed to determine differences between the three groups using a voxel‐wise threshold of p < 0.001 and cluster‐extent threshold of 272 mm3 (FWE<0.05).

Results

In comparison with OHCs, both PDN and PDSI groups demonstrated significant differences in cortical connectivity with bilateral putamen, bilateral GPe, and right caudate. Compared to the PDN group, the PDSI subjects demonstrated significant differences in cortical connectivity with left putamen and left GPi. PDSI subjects had lower connectivity between the left putamen and left superior temporal gyrus compared to PDN. In addition, PDSI subjects had greater connectivity between left GPi and three cortical regions: left dorsal premotor/laryngeal motor cortex, left angular gyrus, and right angular gyrus.

Conclusions

The present findings suggest that speech impairment in PD is associated with altered cortical connectivity with left putamen and left GPi.
Preoperative administration of eculizumab to prevent surgery‐triggered hemolysis during cesarean section with paroxysmal nocturnal hemoglobinuria
Authors: Li Dongping , Wang Liangcheng , Horiuchi Isao , Kimura Shun‐ichi , Chikazawa Kenro , Kimura Azusa , Sasaki Shigetane , Kuwata Tomoyuki , Takagi Kenjiro
Published: July 2018

Key Clinical message

Eculizumab in pregnancy has been reported to be effective in improving outcomes in patients with paroxysmal nocturnal hemoglobinuria. However, a cesarean section may result in surgery‐triggered hemolysis. An additional dose of eculizumab just prior to delivery is an appropriate choice to prevent postoperative hemolysis.
Postoperative granulomatous peritonitis mimicking abdominal tuberculosis
Authors: Kasper Philipp , Pütz Katharina , Fünger Sarah , Suárez Isabelle , Jung Norma , Alakus Hakan , Bruns Christiane , Rybniker Jan
Published: July 2018

Key Clinical Message

Granulomatous peritonitis represents a rare postoperative complication that should be considered as important differential diagnosis in all patients who present to the hospital with abdominal pain, abdominal tenderness, and fever after abdominal surgery. Clinical distinction from abdominal tuberculosis remains a diagnostic challenge and requires thorough histopathological and microbiological examination.
Mesoporous Graphitic Carbon‐Encapsulated Fe2O3 Nanocomposite as High‐Rate Anode Material for Sodium‐Ion Batteries
Authors: Hou Tianyi , Sun Xiaohong , Xie Dongli , Wang Mingjing , Fan Anran , Chen Yuanyuan , Cai Shu , Zheng Chunming , Hu Wenbin
Published: July 2018

A mesoporous graphitic carbon‐encapsulated Fe2O3 nanocomposite is synthesized as a superior anode material for sodium‐ion batteries. A threefold strategy is adopted to achieve a high rate performance. First, the mesoporous structure with high specific surface area and large pore volume facilitates the transfer of electrolyte and accommodates the large volume change. Secondly, graphitic carbon encapsulation further improves the electronic conductivity of the nanocomposite. Finally, ultrafine Fe2O3 nanocrystals effectively shorten the Na+ diffusion length. Consequently, this nanocomposite exhibits stable and fast Na+ storage, thus leading to excellent rate capability and cyclability. Pseudocapacitive behavior is found to dominate in the redox reactions, accounting for the outstanding rate and cycling performance. In addition, full cells, assembled with O3‐Na0.9[Cu0.22Fe0.30Mn0.48]O2 as cathodes, present good electrochemical performance.
Transition Metal Catalyzed Direct Oxidative Borylation of C—H Bonds
Authors: Jiang Zhong‐Tao , Wang Bi‐Qin , Shi Zhang‐Jie
Published: July 2018

Organoboron is well‐developed and broadly utilized organometallic reagents in organic synthesis due to its extraordinary performances in transition‐metal catalyzed C‐C and C‐X bonds construction. Catalytic C—H borylation and further transformations catalyzed by transition metal catalysts in the absence of oxidants were well studied in decades. However, as known, transition metal catalyzed oxidative C—H borylations were not reviewed up to date. In this article the oxidative borylation of C(sp2)‐H and C(sp3)‐H bonds were summarized and their mechanisms were also accounted.
Clinical study of asbestos‐related lung cancer diagnosed by asbestos medical examination
Authors: Yotsumoto Takuma , Sano Atsushi , Fukuda Tsutomu
Published: July 2018

Aim

People with occupational exposure to asbestos demonstrate a high incidence of lung cancer. Asbestos medical examination for those at risk was implemented as a national policy in Japan. This study aimed to characterize patients with asbestos‐related lung cancer who were diagnosed by these examinations.

Methods

We retrospectively investigated 120 individuals exposed to asbestos who were examined from 2008 to 2016 at our institution. Clinical data, including CT findings and time‐related exposure variables, were evaluated. Each asbestos‐related change was assigned 1 point if present, and the scores were compared between patients with and without asbestos‐related lung cancer using the Mann‐Whitney U test and Fisher's exact test.

Results

Five patients were diagnosed with lung cancer, and four underwent surgical treatment. At the time of writing, three of four operated patients were alive without recurrence, with a similar prognosis to patients with lung cancer unrelated to asbestos. Average scores for asbestos‐related findings on CT Scan were 1.8 (9/5) for patients with lung cancer and 0.79 (91/115) for those without lung cancer.

Conclusion

Patients with lung cancer had significantly more asbestos‐related changes on CT scan than those without lung cancer. Concurrent calcified plaque and interstitial changes might be a predictor of lung cancer incidence. Although further investigation with a larger study group is needed, regular medical examination and CT scan every 6 months might contribute to the early detection of lung cancer with asbestos‐related changes on CT.
Internal Redox Polarity of an Individual G. sulfurreducens Bacterial Cell Attached to an Inorganic Substrate
Authors: Lebedev Nikolai , Yates Matthew D. , Griva Igor , Tender Leonard M.
Published: July 2018

Invited for this month cover is the work of a multidisciplinary dynamic team from the U.S. Naval Research Laboratory, consisting of the biophysicist Dr. Nikolai Lebedev, the bioengineer Dr. Matthew Yates, the electrochemist Dr. Leonard Tender and the mathematician Prof. Igor Griva from George Mason University. The image shows how the information about the cell environment is coded inside an individual bacterium and how the researchers can read this code with a Raman microscope. Read the full text of the Article at 10.1002/cphc.201800289.
Inside the mind of the client: An analysis of litigants' decision criteria for choosing procedures
Authors: Shestowsky Donna
Published: July 2018

This article presents findings from the first longitudinal study to ask civil litigants prospectively what criteria they plan to consider when selecting legal procedures and then retroactively assess the criteria used to make those decisions. The most commonly referenced ex ante criteria are lawyer's advice, cost, and time. The retrospective reasons also include these factors, but the list is narrower and more practical. Litigants who initially listed a desire to reduce costs or follow their lawyers' advice were later significantly more likely to report using procedures for these reasons, suggesting the stability of these criteria. However, the same stability did not manifest for other criteria. Implications for improving protocols for counseling litigants about procedure are discussed.
Environmental responsibility, market valuation, and firm characteristics: Evidence from China
Authors: Hu Junnan , Wang Shujing , Xie Feixue
Published: July 2018

Using a large panel of listed firms in China from 2010 to 2015, this study investigates the valuation effect of corporate environmental responsibility (CER) and firm characteristics that influence such an effect. We implement the ordinary least squares and the fixed effects panel regressions as well as the two‐stage least squares regressions that control for potential endogeneity. We find that CER has a significantly positive effect on firm performance. The positive effect is more pronounced for firms in highly polluting industries, with high asset tangibility and with low state ownership. Furthermore, firms with high ownership concentration and low managerial ownership tend to benefit more from their environmentally responsible activities, suggesting that enhanced environmental engagement may serve as a strategic tool in reducing the negative effects of agency cost and weak corporate governance on firm valuation. Our results are robust to alternative measures of performance (Tobin's Q and return on assets).
Prevention of biofilm re‐development on Ti‐6Al‐4V alloy by cometary discharge with a metallic grid
Authors: Vaňková Eva , Válková Markéta , Kašparová Petra , Masák Jan , Scholtz Vladimír , Khun Josef , Julák Jaroslav
Published: July 2018

The influence of a non‐thermal plasma (NTP) on the gram‐negative bacteria Escherichia coli and Pseudomonas aeruginosa, the gram‐positive bacterium Staphylococcus epidermidis, and the yeast Candida albicans grown on agar or in the biofilm form was compared. NTP was produced by a DC cometary discharge. The biofilms were grown on the surface of Ti‐6Al‐4V alloy often used in the manufacture of prosthetic implants. The exposure by NTP not only inhibited the surface growth of microorganisms in agar cultures but also significantly suppressed the viability of bacteria and yeast in biofilms and prevented its re‐developed from persistent cells remaining in the lower layers of the biofilm. An almost complete prevention of biofilm re‐development was achieved in the case of S. epidermidis; other microorganisms displayed substantial lowering of biofilm biomass and its metabolic activity.