bluuebunny/crossref_metadata_2025 huggingface dataset:
Approaching Ultrastable High‐Rate Li–S Batteries through Hierarchically Porous Titanium Nitride Synthesized by Multiscale Phase Separation
Authors: Lim Won‐Gwang , Jo Changshin , Cho Ara , Hwang Jongkook , Kim Seongseop , Han Jeong Woo , Lee Jinwoo
Published: November 2018

Porous architectures are important in determining the performance of lithium–sulfur batteries (LSBs). Among them, multiscale porous architecutures are highly desired to tackle the limitations of single‐sized porous architectures, and to combine the advantages of different pore scales. Although a few carbonaceous materials with multiscale porosity are employed in LSBs, their nonpolar surface properties cause the severe dissolution of lithium polysulfides (LiPSs). In this context, multiscale porous structure design of noncarbonaceous materials is highly required, but has not been exploited in LSBs yet because of the absence of a facile method to control the multiscale porous inorganic materials. Here, a hierarchically porous titanium nitride (h‐TiN) is reported as a multifunctional sulfur host, integrating the advantages of multiscale porous architectures with intrinsic surface properties of TiN to achieve high‐rate and long‐life LSBs. The macropores accommodate the high amount of sulfur, facilitate the electrolyte penetration and transportation of Li+ ions, while the mesopores effectively prevent the LiPS dissolution. TiN strongly adsorbs LiPS, mitigates the shuttle effect, and promotes the redox kinetics. Therefore, h‐TiN/S shows a reversible capacity of 557 mA h g−1 even after 1000 cycles at 5 C rate with only 0.016% of capacity decay per cycle.
Ligand‐Free Iridium‐Catalyzed Dehydrogenative ortho C−H Borylation of Benzyl‐2‐Pyridines at Room Temperature
Authors: Yang Yuhuan , Gao Qian , Xu Senmiao
Published: November 2018

A convenient and ligand‐free iridium‐catalyzed dehydrogenative ortho C−H borylation of benzyl‐2‐pyridines has been developed. The reaction proceeds smoothly at room temperature using pinacolborane as a borylating reagent in the presence of catalytic amount of [IrOMe(COD)]2. The reaction is compatible with many functional groups, providing a vast array of ortho borylated products in moderate to excellent yields with excellent selectivities.

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Biofunctionalized Materials Featuring Feedforward and Feedback Circuits Exemplified by the Detection of Botulinum Toxin A
Authors: Wagner Hanna J. , Kemmer Svenja , Engesser Raphael , Timmer Jens , Weber Wilfried
Published: November 2018

Feedforward and feedback loops are key regulatory elements in cellular signaling and information processing. Synthetic biology exploits these elements for the design of molecular circuits that enable the reprogramming and control of specific cellular functions. These circuits serve as a basis for the engineering of complex cellular networks, opening the door for numerous medical and biotechnological applications. Here, a similar principle is applied. Feedforward and positive feedback circuits are incorporated into biohybrid polymer materials in order to develop signal‐sensing and signal‐processing devices. This concept is exemplified by the detection of the proteolytic activity of the botulinum neurotoxin A. To this aim, site‐specific proteases are incorporated into receiver, transmitter, and output materials, and their release, diffusion, and/or activation are wired according to a feedforward or a positive feedback circuit. The development of a quantitative mathematical model enables analysis and comparison of the performance of both systems. The flexible design could be easily adapted to detect other toxins or molecules of interest. Furthermore, cellular signaling or gene regulatory pathways could provide additional blueprints for the development of novel biohybrid circuits. Such information‐processing, material‐embedded biological circuits hold great promise for a variety of analytical, medical, or biotechnological applications.
Switchable Two‐Terminal Transparent Optoelectronic Devices Based on 2D Perovskite
Authors: Kumar Mohit , Patel Malkeshkumar , Park Dae Young , Kim Hong‐Sik , Jeong Mun Seok , Kim Joondong
Published: November 2018

A switch‐like structure that can be turned on/off with photons is considered necessary for most optoelectronic devices, such as phototransistors and photodetectors. However, developing a single device whose photoresponse can be modulated without changing the measuring voltage or illuminating light is challenging, and yet to be achieved. In this work, a conceptually new 2D perovskite‐based fully transparent two‐terminal optoelectronic device that can be turned on/off with a short electric pulse without any further change in the measuring conditions, such as the illuminating photon or applied voltage is proposed and demonstrated. The device exhibits loop opening in the current–voltage characteristics, which is utilized to design the novel electrically triggered optoelectronic device. The photocurrent of the device can be modulated from zero to 2.2 mA using a simple voltage pulse. Further, a responsivity of 550 mA W−1 and detectivity of 2.16 × 1010 Jones are measured in the on‐state. Potentially, the approach opens a new avenue for the design of two‐terminal advanced highly transparent optoelectronic devices, such as smart windows and transparent image sensors.
Fabrication of Low‐Tortuosity Ultrahigh‐Area‐Capacity Battery Electrodes through Magnetic Alignment of Emulsion‐Based Slurries
Authors: Li Linsen , Erb Randall M. , Wang Jiajun , Wang Jun , Chiang Yet‐Ming
Published: November 2018

High energy‐density, low‐cost batteries are critically important to a variety of applications ranging from portable electronics to electric vehicles (EVs) and grid‐scale storage. While tremendous research effort has been focused on new materials or chemistries with high energy‐density potential, design innovations such as low‐tortuosity thick electrodes are another promising path toward higher energy density and lower cost. Growing demand for fast‐charging batteries has also highlighted the need for negative electrodes that can accept high rate charging without metal deposition; low tortuosity can be a benefit in this regard. However, a general and scalable fabrication method for low‐tortuosity electrodes is currently lacking. Here an emulsion‐based, magnetic‐alignment approach to producing thick electrodes (>400 µm thickness) with ultrahigh areal capacity (up to ≈14 mAh cm−2 vs 2–4 mAh cm−2 for conventional lithium ion) is reported. The process is demonstrated for LiCoO2 and meso‐carbon microbead graphite. The LiCoO2 cathodes are confirmed to have low tortuosity via DC‐depolarization experiments and deliver high areal capacity (>10 mAh cm−2) in galvanostatic discharge tests at practical C‐rates and model EV drive‐cycle tests. This simple fabrication method can potentially be applied to many other active materials to enable thick, low‐tortuosity electrodes.
Long‐ and short‐term responses ofAsclepiasspecies differ in respect to fire, grazing, and nutrient addition
Authors: Ricono Angela , Dixon Robin , Eaton Isabel , Brightbill Caroline M. , Yaziji Yahya , Puzey Joshua R. , Dalgleish Harmony J.
Published: November 2018

Premise of the Study

The tallgrass prairie ecosystem has experienced a dramatic reduction over the past 150 yr. This reduction has impacted the abundance of native grassland species, including milkweeds (Asclepias).

Methods

We used two long‐term (27 yr) data sets to examine how fire, grazing, and nutrient addition shape milkweed abundance in tallgrass prairie. We compared these results to those of a greenhouse experiment that varied nutrient levels in the absence of competition, herbivory, and mutualistic relationships.

Key Results

Asclepiasspecies exhibited broad patterns in response to burning regimes that did not include grazing, but experienced more species‐specific patterns in other combinations.Asclepias syriacawas the only species to increase in abundance in plots that included burning and nutrient addition. In the greenhouse we found that nitrogen significantly increased biomass, while no effect of phosphorus was detected.

Conclusions

These results indicate thatA. syriacawill do best in settings with high nutrient loads, low competition, and no grazers. These characteristics define a small portion of the tallgrass prairie but exemplify modern agricultural settings, which have replaced prairies. However, other milkweeds examined did not share this pattern, which indicates that milkweed species will respond differently when exposed to agricultural settings, with some less able to cope with land conversion to pasture or row‐crop agriculture.
Thiol−Ene Reaction: Synthetic Aspects and Mechanistic Studies of an Anti‐Markovnikov‐Selective Hydrothiolation of Olefins
Authors: Sinha Arun K. , Equbal Danish
Published: November 2018

In synthetic organic chemistry, the anti‐Markovnikov thiol−ene click (TEC) reaction has emerged as a powerful and widely used approach to build carbon−sulfur (C−S) bonds owing to several inherent benefits, including simple synthetic procedures, high atom economy with no side products, and easy purification, which results in the formation of linear thioethers in high yield under mild reaction conditions. These TEC reactions have numerous trapping applications in the field of nanoengineering, polymer science, and in medicinal chemistry for the synthesis of many drugs and bioactive molecules. This present review highlights the diversity of TEC reaction in terms of substrates, catalysts and mechanistic studies towards the generation of highly selective anti‐Markovnikov adduct under metal‐free, metal‐catalyzed, and photo‐induced reaction conditions.
Changes in the clinical and histological characteristics of Chinese chronic rhinosinusitis with nasal polyps over 11 years
Authors: Wang Weiqing , Gao Yali , Zhu Zhenzhen , Zha Yang , Wang Xiaowei , Qi Fang , Zhou Liangrui , Pang Junyi , Gao Zhiqiang , Lv Wei
Published: November 2018

Background

Traditionally, it was believed that chronic rhinosinusitis with nasal polyps (CRSwNP) demonstrated less eosinophilic and more neutrophilic inflammation in China compared to North America and Europe. However, inflammatory patterns may change over time. The study aimed to analyze the changing trends in the clinical and histological characteristics of CRSwNP over time in China.

Methods

A total of 115 consecutive CRSwNP patients from 2003 to 2005 and 114 consecutive CRSwNP patients from 2014 to 2016 were enrolled in this retrospective study. The clinical and histological data were compared between patients from the 2 time periods.

Results

The percentage of eosinophils in nasal polyp tissue increased, and the percentage of neutrophils and total inflammatory cell count decreased, over 11 years. The proportion of eosinophilic CRSwNP significantly increased from 59.1% to 73.7% over 11 years. The proportion of neutrophils and the total inflammatory cell count in nasal polyps decreased, and the proportion of eosinophilic CRSwNP patients using intranasal corticosteroids 1 month before surgery increased remarkably over 11 years. Moreover, eosinophilic CRSwNP patients had better compliance with intranasal corticosteroid use than non‐eosinophilic CRSwNP patients, and patients with comorbid allergic rhinitis and asthma had better compliance with intranasal corticosteroid use than patients without those conditions.

Conclusion

Eosinophilic CRSwNP, which was previously a minor subtype in East Asians, has increased remarkably in incidence to become the predominant CRSwNP subtype in Beijing, China, indicating that rhinologists should place greater emphasis on its diagnosis and treatment.
Impaired eating‐related quality of life in chronic rhinosinusitis
Authors: Rowan Nicholas R. , Soler Zachary M. , Storck Kristina A. , Othieno Florence , Ganjaei Kimia G. , Smith Timothy L. , Schlosser Rodney J.
Published: November 2018

Background

Despite the tremendous burden of smell and taste dysfunction in patients with chronic rhinosinusitis (CRS), objective measures of smell and taste fail to fully account for eating‐related disruptions in CRS patient quality of life (QOL). In this study we sought to investigate the driving force behind impaired eating‐related QOL in CRS patients.

Methods

Adult CRS patients were prospectively enrolled and answered a series of surveys relating to smell, taste, overall sinus‐specific QOL, and depression. Patients with both smell‐related and taste‐related eating complaints were considered to have impaired eating‐related QOL. Clinical demographics, objective chemosensory scores, and endoscopy scores were collected.

Results

Seventy patients were enrolled and 23% showed impaired eating‐related QOL. In multivariable analyses, patients with aspirin‐exacerbated respiratory disease (AERD) showed 10.7 times higher odds of impaired eating‐related QOL (odds ratio [OR] 10.72; 95% confidence interval [CI], 1.09 to 105.09; p = 0.042); meanwhile, for every 1‐point increase in depression scores, the odds of impaired eating‐related QOL increased by 1.3 (OR 1.31; 95% CI, 1.10 to 1.57; p = 0.003). For every 1‐point decrease in orthonasal olfactory threshold, the odds of impaired eating‐related QOL increased by 1.9 times (OR 1.85; 95% CI, 1.14 to 3.00; p = 0.013). Symptom scores, polyp status, endoscopic scores, and other olfactory measures did not remain significant after adjusting for other variables in forward‐selection multivariable modeling.

Conclusion

Disruptions in eating‐related QOL cannot be fully explained by objective smell or taste testing alone. We identified AERD and depression as independent risk factors for greater odds of impaired eating‐related QOL in CRS. Improved orthonasal threshold scores were independently associated with better eating‐related QOL.
Spatially Resolved Covalent Functionalization Patterns on Graphene
Authors: Valenta Leoš , Kovaříček Petr , Valeš Václav , Bastl Zdeněk , Drogowska Karolina A. , Verhagen Timotheus A. , Cibulka Radek , Kalbáč Martin
Published: November 2018

Spatially resolved functionalization of 2D materials is highly demanded but very challenging to achieve. The chemical patterning is typically tackled by preventing contact between the reagent and material, which brings various accompanying challenges. Photochemical transformation on the other hand inherently provides remote high spatiotemporal resolution using the cleanest reagent—a photon. Herein, we combine two competing reactions on a graphene substrate to create functionalization patterns on a micrometer scale via the Mitsunobu reaction. The mild reaction conditions allow introduction of covalently dynamic linkages, which can serve as reversible labels for surface‐ or graphene‐enhanced Raman spectroscopy characterization of the patterns prepared. The proposed methodology thus provides a pathway for local introduction of arbitrary functional groups on graphene.
Modelling effects of invasive species and drought on crayfish extinction risk and population dynamics
Authors: Yarra Allyson N. , Magoulick Daniel D.
Published: November 2018

Hydrological alteration, which may be exacerbated by climate change, is known to facilitate aquatic species invasion. Altered hydrology, invasive species, and the additive effects of these stressors pose a threat to aquatic biodiversity.

Understanding extinction risk in the context of these stressors is crucial for prioritizing conservation efforts. As case studies, three narrow‐ranged endemic crayfish species of conservation concern (Faxonius marchandi, Faxonius roberti, and Cambarus hubbsi) in the Ozark Highlands of Arkansas and Missouri, USA, were used to examine the effects of invasive species and drought on crayfish population dynamics.

The objectives of this study were to model the population dynamics of these imperilled species, assess how these populations may be affected under increased invasion effects and intensified drought, determine potential refuge effects, and examine the sensitivity of quasi‐extinction to model parameters.

ramas‐metapop was used to construct stage‐based demographic models. Terminal extinction risk, median time to quasi‐extinction, and metapopulation occupancy were used to assess population viability under different scenarios.

Cambarus hubbsi appears to be highly susceptible to decline if survival rates are reduced by simulated drought, as they have low reproductive potential and mature slowly. Models indicated that potential refuges allow F. roberti and C. hubbsi to persist, even when invasion and drought effects were extreme. Conversely, barriers to dispersal for F. marchandi led to reduced quasi‐extinction times and the greatest extinction risk under most invasion scenarios. Quasi‐extinction was most sensitive to changes in juvenile survival for all species examined, which indicates that improved estimates of stage‐specific demographic parameters for crayfish will improve model predictions.

An increased understanding of the mechanisms of displacement of native crayfish by invasive crayfish is needed for most crayfish species. Limiting the spread of invasive species, maintaining natural habitat and hydrological regimes, and gaining insight into life histories and demographic parameters will increase the ability to conserve endemic and imperilled crayfish.
Multi‐Omics Study on the Impact of Cysteine Feed Level on Cell Viability and mAb Production in a CHO Bioprocess
Authors: Ali Amr S. , Raju Ravali , Kshirsagar Rashmi , Ivanov Alexander R. , Gilbert Alan , Zang Li , Karger Barry L.
Published: November 2018

There is continual demand to maximize CHO cell culture productivity of a biotherapeutic while maintaining product quality. In this study, a comprehensive multi‐omics analysis is performed to investigate the cellular response to the level of dosing of the amino acid cysteine (Cys) in the production of a monoclonal antibody (mAb). When Cys feed levels are insufficient, there is a significant decrease in protein titer. Multi‐omics (metabolomics and proteomics, with support from RNAseq) is performed over the time course of the CHO bioprocess producing an IgG1 mAb in 5 L bioreactors. Pathway analysis reveals that insufficient levels of Cys in the feed lead to Cys depletion in the cell. This depletion negatively impacts antioxidant molecules, such as glutathione (GSH) and taurine, leading to oxidative stress with multiple deleterious cellular effects. In this paper, the resultant ER stress and subsequent apoptosis that affects cell viability and viable cell density has been considered. Key metabolic enzymes and metabolites are identified that can be potentially monitored as the process progresses and/or increased in the cell either by nutrient feeding or genetic engineering. This work reinforces the centrality of redox balance to cellular health and success of the bioprocess as well as the power of multi‐omics to provide an in‐depth understanding of the CHO cell biology during biopharmaceutical production.
Exploring the effects of institutional pressures on the implementation of environmental management accounting: Do top management support and perceived benefit work?
Authors: Wang Shanyong , Wang Hualong , Wang Jing
Published: November 2018

Environmental management accounting (EMA) has been regarded as an effective way to deal with environmental issues and economic performance. On the basis of institutional theory, this research aims to examine the effects of institutional pressures on the implementation of EMA and how such effects are affected by top management support and perceived benefit. Data were collected from the manufacturing firms in the Yangtze River Delta using questionnaire survey method. The results indicated that coercive pressure and normative pressure positively and significantly affect the implementation of EMA whereas mimetic pressure has no significant effect. Furthermore, top management support and perceived benefit play different moderating roles in the relationships between institutional pressures and the implementation of EMA. Top management support and perceived benefit positively moderate the relationships between coercive pressure, normative pressure, and the implementation of EMA although negatively moderate the relationship between mimetic pressure and the implementation of EMA. On the basis of the findings, policy implications and suggestions for future research are discussed.
Reassessing measures of sustainable firm performance: A consultant's guide to identifying hidden costs in corporate disclosures
Authors: Smith William L. , Hillon Yue Cai , Liang Yanni
Published: November 2018

Strategy, management, corporate social responsibility, critical accounting, and other business researchers frequently utilize financial metrics such as return on assets, return on equity, and return on sales as proxy measures for the financial performance of firms. Large data sets offer convenience but exclude the textual data of corporate disclosures that offers critical insight into specific executive actions and social and environmental outcomes. This study looks at the detrimental consequences of the prevalent practice of relying on macrofinancial metrics as measures of firm performance. Insight from the socioeconomic approach to management (SEAM) is then applied to help an external analyst develop the perspective of an internal consultant to identify hidden costs in corporate disclosures. An extensive case on former CEO Robert Nardelli's tenure at Home Depot is presented as an example of applied SEAM theory to explore how a causal network of dysfunctions can be traced through publicly available financial disclosures. The management discussion and analysis as well as the executive incentive compensation formulas serve as a roadmap to discover hidden costs. The study offers a critical perspective of financial disclosures to allow researchers to externally diagnose dysfunctions sooner rather than years later, an insight formerly only available to internal consultants.
Promising clinical outcomes of sequential and “Sandwich” chemotherapy and extended involved‐field intensity‐modulated radiotherapy in patients with stage IE/IIE extranodal natural killer/T‐cell lymphoma
Authors: Wang Han‐yu , Niu Shao‐qing , Yang Yun‐ying , Li Yi‐yang , Chen Hong‐bo , Zhang Yu‐jing
Published: November 2018

Background

The optimal treatment for the rare subtype of non‐Hodgkin lymphoma, extranodal natural killer/T‐cell lymphoma (ENKTL), nasal‐type, has not been clearly defined. The purpose of the study was to investigate the efficacy of sequential and “Sandwich” chemotherapy and extended involved‐field intensity‐modulated radiotherapy (IMRT) in patients with stage IE/IIE extranodal ENKTL, nasal‐type.

Methods

One hundred and fifty‐five patients with stage IE/IIE nasal‐type ENKTL were enrolled in the study, including 99 patients treated with sequential chemotherapy and extended involved‐field IMRT (SCRT) and 56 patients with “Sandwich” chemotherapy and extended involved‐field IMRT and chemotherapy (SCRCT). All patients were treated with extended involved‐field IMRT with median dose of 54.6 Gy to the primary tumor and positive lymph nodes. Ninety‐four patients had Ann Arbor stage IE disease, and 61 patients had stage IIE disease.

Results

The 5‐year rates of loco‐regional recurrence (LRR), progression‐free survival (PFS), and overall survival (OS) were 17.0%, 78.5%, and 84.7%, respectively. Univariate analysis revealed that EBV DNA copy after treatment (normal vs elevated level) was significant prognostic factor for LRR, PFS, and OS (P < 0.001); therapeutic method (SCRT vs SCRCT) was significant prognostic factor for PFS (71.0% vs 91.8%, P = 0.011), but there was no significant effect on 5‐year LRR and OS (22.2% vs 8.2%, P = 0.051 for LRR; 80.9% vs 91.8%, P = 0.199 for OS).

Conclusions

Compared with SCRT, SCRCT was significantly associated with higher PFS rates and showed a trend toward improved loco‐regional control. EBV DNA copy after treatment is a good index for recurrence and prognosis for stage IE/IIE ENKTL patients.
Risk and prognostic factors for endometrial carcinoma after diagnosis of breast or Lynch‐associated cancers—A population‐based analysis
Authors: Johnatty Sharon E. , Stewart Colin J. R. , Smith Deborah , Buchanan Daniel , Leung Yee , Oehler Martin K. , Brand Alison , Webb Penelope M. , Spurdle Amanda B.
Published: November 2018

We hypothesized that endometrial carcinoma (EC) patients with a prior cancer diagnosis, after accounting for EC arising after tamoxifen‐treated prior breast carcinoma, are more likely to have an underlying genetic basis. We used information from a population‐based study to compare measured risk factors, tumor characteristics, survival, and known mismatch repair (MMR) pathogenic variant status for EC subgroups according to prior diagnosis of cancer (none, breast cancer tamoxifen‐treated or not, Lynch Syndrome (LS)‐associated cancer). Family history of any cancer was increased for EC cases with prior breast cancer, both tamoxifen treated (P = 0.005) and untreated (P = 0.01). EC cases with prior LS‐associated cancer more often reported family history of LS‐associated cancer (P = 0.04) and breast cancer (P = 0.05). EC patients with a germline pathogenic MMR gene variant were more likely to report a prior cancer than cases with a MMR proficient tumor (P = 0.0001), but more than half (54.5%) of MMR carriers reported no prior cancer. Women developing EC after tamoxifen treatment for breast cancer were significantly more likely to develop EC of malignant mixed mullerian tumor subtype (13.2% vs 2.6%, P = 1.3 × 10−6), present with stage IV disease (8.8% vs 1.2%, P = 1.6 × 10−6), and have poorer survival (HRadj 1.96; P = 0.001). While report of prior cancer is an indicator of MMR pathogenic variant status, molecular analysis of all ECs at diagnosis is warranted to detect all patients with LS. Results also indicate the importance of longer‐term monitoring of women treated with tamoxifen for symptoms of EC, and the need for studies assessing the biological mechanism underlying the poorer prognosis of this subset of EC patients.
Mitochondrion‐Targeting Identification of a Fluorescent Apoptosis‐Triggering Molecule by Mass Spectrometry Elucidates Drug Tracking
Authors: Zhang Guohai , Li Liangping , Shi Zhenhao , Yang Yang , Wu Yiming , Song Huanhuan , Long Jingxian , Lu Xing , Zeng Shulan , Qin Jiangke , Sun Hongbin , Chen Zhenfeng , Liang Hong , Peng Yan
Published: November 2018

The real‐time tracking of localization and dynamics of small molecules in organelles helps to understand their function and identification of their potential targets at subcellular resolution. To identify the mitochondrion‐targeting effects of small molecules (NA‐17 and NA‐2a) in cancer cells, we used mass spectrometry to study their distribution and accumulation in mitochondria and in the surrounding cytoplasm thus enabling tracing of action processes of therapeutic compounds. Colocalization analysis with the aid of imaging agents suggests that both NA‐17 and NA‐2a display mitochondrion‐targeting effects. However, MS analysis reveals that only NA‐2a displays both a mitochondrion‐targeting effect and an accumulation effect, whereas NA‐17 only distributes in the surrounding cytoplasm. A combination of mitochondrion imaging, immunoblotting, and MS analysis in mitochondria indicated that NA‐17 neither has the ability to enter mitochondria directly nor displays any mitochondrion‐targeting effect. Further studies revealed that NA‐17 could not enter into mitochondria even when the mitochondrial permeability in cells changed after NA‐17 treatment, as was evident from reactive oxygen species (ROS) generation and cytochrome c release. In the process of cellular metabolism, NA‐17 itself is firmly restricted to the cytoplasm during the metabolic process, but its metabolites containing fluorophores could accumulate in mitochondria for cell imaging. Our studies have furnished new insights into the drug metabolism processes.
Intercalating Electron Dyes for TEM Visualization of DNA at the Single‐Molecule Level
Authors: Kabiri Yoones , Angelin Alessandro , Ahmed Ishtiaq , Mutlu Hatice , Bauer Jens , Niemeyer Christof M. , Zandbergen Henny , Dekker Cees
Published: November 2018

Staining compounds containing heavy elements (electron dyes) can facilitate the visualization of DNA and related biomolecules by using TEM. However, research into the synthesis and utilization of alternative electron dyes has been limited. Here, we report the synthesis of a novel DNA intercalator molecule, bis‐acridine uranyl (BAU). NMR spectroscopy and MS confirmed the validity of the synthetic strategy and gel electrophoresis verified the binding of BAU to DNA. For TEM imaging of DNA, two‐dimensional DNA origami nanostructures were used as a robust microscopy test object. By using scanning transmission electron microscopy (STEM) imaging, which is favored over conventional wide‐field TEM for improved contrast, and therefore, quantitative image analysis, it is found that the synthesized BAU intercalator can render DNA visible, even at the single‐molecule scale. For comparison, other staining compounds with a purported affinity towards DNA, such as dichloroplatinum, cisplatin, osmium tetroxide, and uranyl acetate, have been evaluated. The STEM contrast is discussed in terms of the DNA–dye association constants, number of dye molecules bound per base pair, and the electron‐scattering capacity of the metal‐containing ligands. These findings pave the way for the future development of electron dyes with specific DNA‐binding motifs for high‐resolution TEM imaging.
Triple Orthogonal Labeling of Glycans by Applying Photoclick Chemistry
Authors: Schart Verena F. , Hassenrück Jessica , Späte Anne‐Katrin , Dold Jeremias E. G. A. , Fahrner Raphael , Wittmann Valentin
Published: November 2018

Bioorthogonal labeling of multiple biomolecules is of current interest in chemical biology. Metabolic glycoengineering (MGE) has been shown to be an appropriate approach to visualizing carbohydrates. Here, we report that the nitrile imine–alkene cycloaddition (photoclick reaction) is a suitable ligation reaction in MGE. Using a mannosamine derivative with an acrylamide reporter group that is efficiently metabolized by cells and that quickly reacts in the photoclick reaction, we labeled sialic acids on the surface of living cells. Screening of several alkenes showed that a previously reported carbamate‐linked methylcyclopropene reporter that is well suited for the inverse‐electron‐demand Diels–Alder (DAinv) reaction has a surprisingly low reactivity in the photoclick reaction. Thus, for the first time, we were able to triply label glycans by a combination of DAinv, photoclick, and copper‐free click chemistry.
Surface Atomic Regulation of Core–Shell Noble Metal Catalysts
Authors: Ge Jingjie , Li Zhijun , Hong Xun , Li Yadong
Published: November 2018

Core–shell noble metal catalysts have gained significant attention in the past few decades, as they not only reduce the use of noble metals effectively but also exhibit unique properties derived from the synergistic effect between core and shell metals. In particular, regulating the surface structure of shells to maximize the atomic utilization efficiency of noble metals is critically important. Controlling the shell thickness of noble metal catalysts at the atomic level as an efficient approach to realize this goal has been attracting growing attention; this approach involves the formation of ultrathin shells (typically 2–6 atomic layers), monolayers, or even atomically dispersed noble metals embedded in the host metal. These strategies drive the core/support metals to improve the number of active sites and the intrinsic activity of the deposited noble metals remarkably, meanwhile minimizing the usage of noble metals. Herein, recent advances regarding atomic control of the core–shell noble metal catalysts is reviewed, with focus on the surface regulation. First, synthesis methods and surface structures are summarized, and then catalytic applications of these architectures are highlighted.
How Do Substrates Bind to a Bifunctional Thiourea Catalyst? A Vibrational CD Study on Carboxylic Acid Binding
Authors: Kreienborg Nora M. , Merten Christian
Published: November 2018

Invited for the cover of this issue are Nora M. Kreienborg and Christian Merten from Ruhr‐University Bochum. They report a vibrational CD study on substrate binding of a thiourea catalyst during which they have encountered some interesting obstacles. Read the full text of the article at 10.1002/chem.201804230.
Semi‐Rigid Nitroxide Spin Label for Long‐Range EPR Distance Measurements of Lipid Bilayer Embedded β‐Peptides
Authors: Wegner Janine , Valora Gabriele , Halbmair Karin , Kehl Annemarie , Worbs Brigitte , Bennati Marina , Diederichsen Ulf
Published: November 2018

β‐Peptides are an interesting new class of transmembrane model peptides based on their conformationally stable and well‐defined secondary structures. Herein, we present the synthesis of the paramagnetic β‐amino acid β3‐hTOPP (4‐(3,3,5,5‐tetramethyl‐2,6‐dioxo‐4‐oxylpiperazin‐1‐yl)‐d‐β3‐homophenylglycine) that enables investigations of β‐peptides by EPR spectroscopy. This amino acid adds to the, to date, sparse number of β‐peptide spin labels. Its performance was evaluated by investigating the helical turn of a 314‐helical transmembrane model β‐peptide. Nanometer distances between two incorporated β3‐hTOPP labels in different environments were measured by using pulsed electron/electron double resonance (PELDOR/DEER) spectroscopy. Due to the semi‐rigid conformational design, the label delivers reliable distances and sharp (one‐peak) distance distributions even in the lipid bilayer. The results indicate that the investigated β‐peptide folds into a 3.2514 helix and maintains this conformation in the lipid bilayer.
Patients’ information coping styles influence the benefit of a survivorship care plan in the ROGY Care Trial: New insights for tailored delivery
Authors: de Rooij Belle H. , Ezendam Nicole P. M. , Vos M. Caroline , Pijnenborg Johanna M. A. , Boll Dorry , Kruitwagen Roy F. P. M. , van de Poll‐Franse Lonneke V.
Published: November 2018

Background

In efforts to improve the implementation of survivorship care plans (SCPs), the authors assessed whether the impact of SCPs on patient‐reported outcomes differed between patients with an information‐seeking coping style (monitoring) versus those with an information‐avoiding coping style (blunting).

Methods

In the Registration System Oncological Gynecology (ROGY) Care Trial, 12 hospitals in the Netherlands were randomized to deliver SCP care or usual care. All patients with newly diagnosed endometrial and ovarian cancer in the SCP care arm received an SCP that was generated automatically by their oncology provider through the web‐based ROGY registration system. Outcomes (satisfaction with information provision and care, illness perceptions, and health care use) were measured directly after initial treatment and after 6, 12, and 24 months. Information coping style was measured at 12 months after initial treatment.

Results

Among patients who had a monitoring coping style (N = 123), those in the SCP care arm reported higher satisfaction with information provision (mean score: 73.9 vs 63.9, respectively; P = .04) and care (mean score: 74.5 vs 69.2, respectively; P = .03) compared with those in the usual care arm. Among patients who had a blunting coping style (N = 102), those in the SCP care arm reported a higher impact of the disease on life (mean score: 5.0 vs 4.5, respectively; P = .02) and a higher emotional impact of the disease (mean score: 5.4 vs 4.2, respectively; P = .01) compared with those in the usual care arm.

Conclusions

SCPs may be beneficial for patients who desire information about their disease, whereas SCPs may be less beneficial for patients who avoid medical information, suggesting a need for tailored SCP delivery to improve survivorship care.
Leveraging patient‐reported outcomes data to inform oncology clinical decision making: Introducing the FACE‐Q Head and Neck Cancer Module
Authors: Cracchiolo Jennifer R. , Klassen Anne F. , Young‐Afat Danny A. , Albornoz Claudia R. , Cano Stefan J. , Patel Snehal G. , Pusic Andrea L. , Matros Evan
Published: November 2018

Background

Existing patient‐reported outcome measures (PROMs) used to assess patients with head and neck cancer have methodologic and content deficiencies. Herein, the development of a PROM that meets a range of clinical and research needs across head and neck oncology is described.

Methods

After development of the conceptual framework, which involved a literature review, semistructured patient interviews, and expert input, patients with head and neck cancer who were treated at Memorial Sloan Kettering Cancer Center were recruited by their surgeon. The FACE‐Q Head and Neck Cancer Module was completed by patients in the clinic or was sent by mail. Rasch measurement theory analysis was used for item selection for final scale development and to examine reliability and validity. Scale scores for surgical defect and adjuvant therapy were compared with the cohort average to assess clinical applicability.

Results

The sample consisted of 219 patients who completed the draft scales. Fourteen independently functioning scales were analyzed. Item fit was good for all 102 items, and all items had ordered thresholds. Scale reliability was acceptable (person separation index was >0.75 for all scales; Cronbach α values were >.87 for all scales; test‐retest ranged from 0.86 to 0.96). The scales performed well in a clinically predictable way, demonstrating functional and psychosocial differences across disease sites and with adjuvant therapy.

Conclusions

The scales forming the FACE‐Q Head and Neck Cancer Module were found to be clinically relevant and scientifically sound. This new PROM now is validated and ready for use in research and clinical care.
Design and implementation of colour texture‐based multiple object detection using morphological gradient approach
Authors: Kandavalli Michael Angelo , Abraham Lincon S.
Published: November 2018

Non‐rigid moving multiple objects detection and tracking play an important role in intelligent video surveillance system, autonomous navigation, and activity analysis. Closed Circuit Television (CCTV) systems are deployed in numerous areas such as airports, traffic intersections, underground stations, mass events, mall, schools, and organisations for security and public surveillance. Although these cameras record continuous video 24x7, it is a human constraint to manually monitor all events such as crime, terrorism, hideous, suspicious activities, the positioning of the vehicle, and fire recorded from a number of cameras. Moreover, problems like dynamic background, the creation of ghost, sensor noise, varying illumination, and colour and compression artefacts affect effective detection of multiple moving objects. This study presents an effective approach named as enhanced Fractal Texture Analysis with KNN classifier (FTAKC) for tracking and detection of multiple objects from a video sequence. The proposed approach comprises three main phases, namely, detection of moving object, tracking of the object (enhanced Fractal Texture Analysis), and behaviour analysis for activity recognition (KNN classifier). The image feature has been extracted based on colour, texture, and geometry were used to identify and track multiple objects in video frames, and Problem domain knowledge rules were applied to distinguish normal or anomalous activities as well as behaviours. Edge detection algorithm (Intersection over Union (IoU) threshold to determine possible edge connections) was applied toward enhancing the illumination variation by multi‐block Local Binary Pattern (LBP) temporal‐analysis to do the segmentation. Finally, the efficiency and effectiveness of the proposed approach has been estimated based on the measure of average PSNR, precision, recall, f‐measure, accuracy, and execution time. The Laboratory for Image and Media Understanding (LIMU) dataset has been utilised toward illustrating the robustness of the proposed approach. Furthermore, it evaluated the performance based on the measure of precision, recall, and F‐measure metrics. It has been tentatively demonstrated that the proposed approach is suitable for recognizing multiple moving object with detection accuracy up to 93.56%. The simulated results show that suggested approach is robust, flexible, as well as able to outperform the traditional methods than the present object detection method.
Research on the mass media effects to the learning efficiency based on social agents
Authors: Yue Guo , Girma Getachew Nathan
Published: November 2018

As mass media continue to grow in popularity, it is our premise that technology is a vital part in today's adolescences' success equation. Based on the literature review, there many scholars discussed standpoint from socialization, the positive and negative aspects of socializing agents, adolescents, and their identity formation take significant part of the discussion. Therefore, we tried to do some survey to get the firsthand data and collected the secondhand data to find out how in‐depth impact adolescence’ life by the mass media. Also the paper studies the mass media affected by the empirical analysis, tried to understand how effects to adolescence’ first time contact mass media, and discussion on the mass media using unbalance between the urban and rural areas in developing countries.
Hepatosplenic T‐Cell Lymphoma in an Immunocompetent Male with Central Nervous System Invasion: A Rare Clinical Entity
Authors: Wu Fan , Pan Ying , Wang Huiping , Tao Qianshan , An Furun , Zhang Jiakui , Zhai Zhimin
Published: November 2018

Hepatosplenic T‐cell lymphoma (HSTCL) is a very rare non‐Hodgkin lymphoma with an aggressive clinical course and poor prognosis. Patients of this disease usually presented with hepatosplenomegaly, which can be misdiagnosed or delayed. Bone marrow (BM) and peripheral blood (PB) are frequently involved, however, central nervous system (CNS) involvement is less common. Here, we are reporting an unusual case of hepatosplenic γδ T‐cell lymphoma in a 64‐year‐old man with CNS involvement. Flow cytometry immunophenotyping was proved of great diagnostic contribution. © 2018 International Clinical Cytometry Society
Fine‐needle aspiration cytology of non‐small cell lung carcinoma: A paradigm shift
Authors: Dey Pranab , Ghosh Ratan Kumar
Published: November 2018

Lung carcinoma is one of the commonest causes of cancer related death. Fine‐needle aspiration cytology (FNAC) is a well‐established technique in the diagnosis of various malignant tumors. FNAC is now an important technique in classifying lung carcinomas and also detecting salient mutational changes in lung carcinomas. The judicious use of the various immunological markers such as TTF‐1, p40, CK 5/6, CK 7 and Napsin may help in sub‐classification of non‐small cell lung carcinomas (NSCLC). The mutational changes in epidermal growth factor receptor (EGFR) and ALK genes are needed in targeted therapy of adenocarcinoma of lung. With the help of immunocytochemistry, polymerase chain receptor, fluorescent in situ hybridization and next generation sequencing, one can detect various mutational changes in NSCLC. In this review article, we have discussed the role of cytology and other ancillary techniques to classify lung carcinomas. The important mutational changes in lung carcinoma for targeted therapy have also been discussed in detail.
Access to 1,1′‐Bifunctional Phosphane Iron(0) Complexes via P–N Bond‐Forming Reactions and Selective P‐Functionalizations
Authors: Schmer Alexander , Terschüren Tatjana , Schnakenburg Gregor , Espinosa Ferao Arturo , Streubel Rainer
Published: November 2018

Reaction of Li/Cl phosphinidenoid Fe(CO)4 complex 2 with ammonia and different amines R1,R2NH yielded complexes 3–5 (3: R1 = R2 = H; 4a: R1 = H, R2 = Me; 4b: R1 = H, R2 = iPr; 4c: R1 = H, R2 = tBu; 4d: R1 = H, R2 = allyl; 4e: R1 = H, R2 = Ph; 5: R1 = Me, R2 = Me) having 1,1′‐bifunctional phosphane ligands via formal N–H bond insertion of the phosphorus center. Studies on deprotonation enabled access to the first structurally characterized K/N(H)R phosphinidenoid complex 6. The latter reacted with phosgene to provide selective access to the P‐chloro complex 7. Theoretical calculations provide insight into the mechanism of the formal N–H bond insertion reaction involving a nucleophilic displacement of chloride at phosphorus and a higher molecularity of a stepwise proton transfer mechanism.
A Perspective on Recent Advances in Phosphorene Functionalization and Its Applications in Devices
Authors: Peruzzini Maurizio , Bini Roberto , Bolognesi Margherita , Caporali Maria , Ceppatelli Matteo , Cicogna Francesca , Coiai Serena , Heun Stefan , Ienco Andrea , Benito Iñigo Iglesias , Kumar Abhishek , Manca Gabriele , Passaglia Elisa , Scelta Demetrio , Serrano‐Ruiz Manuel , Telesio Francesca , Toffanin Stefano , Vanni Matteo
Published: November 2018

Phosphorene, the 2D material derived from black phosphorus, has recently attracted a lot of interest for its properties, suitable for applications in materials science. The physical features and the prominent chemical reactivity on its surface render this nanolayered substrate particularly promising for electrical and optoelectronic applications. In addition, being a new potential ligand for metals, it opens the way for a new role of the inorganic chemistry in the 2D world, with special reference to the field of catalysis. The aim of this review is to summarize the state of the art in this subject and to present our most recent results in the preparation, functionalization, and use of phosphorene and its decorated derivatives. We discuss several key points, which are currently under investigation: the synthesis, the characterization by theoretical calculations, the high pressure behavior of black phosphorus, as well as its decoration with nanoparticles and encapsulation in polymers. Finally, device fabrication and electrical transport measurements are overviewed on the basis of recent literature and the new results collected in our laboratories.
Improved Sustainable Ionic Liquid Catalyzed Production of Symmetrical and Non‐Symmetrical Biological Wax Monoesters
Authors: Yıldırım Ayhan , Mudaber Sebghatullah , Öztürk Serkan
Published: November 2018

Biological wax esters are important commercial products used in various industrial and medicinal fields. These valuable compounds can be synthesized via several chemical and enzymatic reactions which have some advantages and more disadvantages. In particular, many strong acid catalysts cause undesirable structural changes in unsaturated fatty acids molecules. In the present study, easily accessible 1‐hexadecyl‐3‐sulfoimidazolium chloride as an ionic liquid is screened as a mild Brønsted acid metal free catalyst for the chemical esterification, or transesterification, of equimolar amounts of long chain fatty acids or fatty acid methyl esters, respectively, with fatty alcohols in a solventless medium. The various parameters affecting the yield of the wax ester are optimized, catalyst reuse studies, and large scale synthesis are also carried out. According to this alternative practical and green process, a series of wax esters (17 examples) are produced readily in good to excellent yields. There is no undesirable geometric cis‐trans isomerization in unsaturated fatty acids under the reaction conditions used. The catalyst is also quite effective when triglycerides are converted directly to the wax esters via transesterification reaction.

Practical Applications: With an effortless and environmentally friendly method developed in this study, various wax esters can be synthesized as valuable industrial materials. In order to synthesis these esters, there is not any restriction for starting compounds. The most important aspect of the developed procedures is that metallic or strong aggressive acidic catalysts are not used compared to existing procedures. It is possible to carry out large‐scale syntheses of esters with high yields.

In the present study, a series of industrial and medical important wax esters are synthesized from renewable sources in a solvent‐free environment using IL‐catalyzed environmentally friendly methods.