bluuebunny/crossref_metadata_2025 huggingface dataset:
A corpus-based approach to contemporary Irish writing: Ross O’Carroll-Kelly’s use of «like» as a discourse marker
Authors: Amador Moreno Carolina P.
Published: January 2018

This paper analyses in quantitative and qualitative terms the representation of the discourse marker like in contemporary Irish English writing. A common feature of contemporary spoken English, the discourse marker like seems to have made its way into the English spoken in Ireland, as portrayed by contemporary Irish authors such as Paul Howard. Howard, whose narrative can be taken as an example of oral writing, has been acclaimed by critics as having an exceptionally fine ear for Dublin English, but what is this acclamation based on? The paper argues that the findings of corpus stylistics (comparative frequencies, distributions, etc.) document in a more systematic way what literary critics and readers may intuitively deduce. By analysing the syntactic and pragmatic behaviour of like in Howard’s fictional discourse, this paper aims to show the value of the combination of computer methodology and literary interpretation in evaluating the representation of fictional dialect.
Two different faces of Cavafy in English: A corpus-assisted approach to translational stylistics
Authors: Pantopoulos Iraklis
Published: January 2018

A translator is seen to leave a personal mark on the text through their stylistic choices and the patterns formed by these choices. This article comprises a case study that uses a specialized comparative corpus containing translations of C.P. Cavafy's canon in order to explore the distinctive stylistic features of Rae Dalven and of Edmund Keeley and Philip Sherrard (working in collaboration), in both quantitative and qualitative terms. Exploring the different approaches to Cavafy's poetry on the stylistic level reveals the stylistic fragmentation of the poet after crossing over into a dominant language and literary market.

Overall word frequencies for each translation are examined, the stylistic features that are prominent in each case are identified, and their significance is considered. Special attention is also paid to the way a stylistic feature belonging to the ‘universal aspects of literature’ is treated by each translator. By foregrounding the translators and their distinct choices, the “homogenization” effects that often characterize translation into a major language are arrested. Instead, the focus falls on the factors that shape each translator's use of language and their impact.
Contrastive analysis and translation study from a corpus linguistics perspective
Authors: Gómez Castejón María Ángeles
Published: January 2018

Previous contrastive studies between the English gerund and its Spanish counterparts present serious limitations in the analysis of these constructions. The main objection is the absence of a cognitive approach. In addition, the traditional characterization of the English gerund seems to be inappropriate to determine its nature. We propose that in order to carry out a contrastive analysis of these constructions, it is absolutely necessary to include a cognitive approach. This approach establishes a valid characterization of the English gerund as well as the relationship between this category and its Spanish counterparts. We also include a translation study. The translation study is not limited to the establishment of equivalence relations between the source and target languages, but it also provides translations techniques observed in the translation product. On the whole, parallel corpora and translated texts prove to be extremely useful for both our contrastive analysis and translation study.
Comparison and other “Modes of Order” in the plays of Bernard Shaw
Authors: Rodríguez Martín Gustavo A.
Published: January 2018

Bernard Shaw is widely regarded as one of the most important playwrights in the English language, ranking often second only to Shakespeare. This literary prominence, however, is not matched by a significant number of stylistic analyses, much more so in the case of linguistically-oriented ones. One of the few studies in Shaviana with a clear stylistic approach is Ohmann’s (1962) monograph. However, it focuses on Shaw’s non-dramatic writings and, due to its publication date, it does not utilize software tools for corpus stylistics. The purpose of this paper is to analyze Bernard Shaw’s use of certain comparative structures in his dramatic writings (what Ohmann calls ‘Modes of Order’ in his book) with the aid of the technical and methodological advances of computer-based stylistics, thus utilizing an innovative outlook because of the combination of stylistics and corpora research.
The role of awareness of repetition during the development of automaticity in a dot-counting task
Authors: Speelman Craig P. , Shadbolt Emma
Published: January 2018

This study examined whether being aware of the repetition of stimuli in a simple numerosity task could aid the development of automaticity. The numerosity task used in this study was a simple counting task. Thirty-four participants were divided into two groups. One group was instructed that the stimuli would repeat many times throughout the experiment. The results showed no significant differences in the way automatic processing developed between the groups. Similarly, there was no correlation between the point at which automatic processing developed and the point at which participants felt they benefitted from the repetition of stimuli. These results suggest that extra-trial features of a task may have no effect on the development of automaticity, a finding consistent with the instance theory of automatisation.
A review of bottom-up vs. top-down control of sponges on Caribbean fore-reefs: what’s old, what’s new, and future directions
Authors: Pawlik Joseph R. , Loh Tse-Lynn , McMurray Steven E.
Published: January 2018

Interest in the ecology of sponges on coral reefs has grown in recent years with mounting evidence that sponges are becoming dominant members of reef communities, particularly in the Caribbean. New estimates of water column processing by sponge pumping activities combined with discoveries related to carbon and nutrient cycling have led to novel hypotheses about the role of sponges in reef ecosystem function. Among these developments, a debate has emerged about the relative effects of bottom-up (food availability) and top-down (predation) control on the community of sponges on Caribbean fore-reefs. In this review, we evaluate the impact of the latest findings on the debate, as well as provide new insights based on older citations. Recent studies that employed different research methods have demonstrated that dissolved organic carbon (DOC) and detritus are the principal sources of food for a growing list of sponge species, challenging the idea that the relative availability of living picoplankton is the sole proxy for sponge growth or abundance. New reports have confirmed earlier findings that reef macroalgae release labile DOC available for sponge nutrition. Evidence for top-down control of sponge community structure by fish predation is further supported by gut content studies and historical population estimates of hawksbill turtles, which likely had a much greater impact on relative sponge abundances on Caribbean reefs of the past. Implicit to investigations designed to address the bottom-up vs. top-down debate are appropriate studies of Caribbean fore-reef environments, where benthic communities are relatively homogeneous and terrestrial influences and abiotic effects are minimized. One recent study designed to test both aspects of the debate did so using experiments conducted entirely in shallow lagoonal habitats dominated by mangroves and seagrass beds. The top-down results from this study are reinterpreted as supporting past research demonstrating predator preferences for sponge species that are abundant in these lagoonal habitats, but grazed away in fore-reef habitats. We conclude that sponge communities on Caribbean fore-reefs of the past and present are largely structured by predation, and offer new directions for research, such as determining the environmental conditions under which sponges may be food-limited (e.g., deep sea, lagoonal habitats) and monitoring changes in sponge community structure as populations of hawksbill turtles rebound.
Propanediols
Authors: Sullivan Carl J. , Kuenz Anja , Vorlop Klaus‐Dieter
Published: January 2018

The article contains sections titled:1.1,2‐Propanediol and Higher Propylene Glycols1.1.Physical Properties1.2.Chemical Properties1.3.Production1.3.1.Chemical Production1.3.2.Biotechnological Production1.4.Quality Specifications1.5.Transportation and Storage1.6.Economic Aspects1.7.Uses1.8.Derivatives2.1,3‐Propanediol2.1.Properties2.2.Production2.2.1.Chemical Production2.2.2.Biotechnological Production2.3.Quality Specifications2.4.Transportation and Storage2.5.Economic Aspects2.6.Uses3.Toxicology
Propionic Acid and Derivatives
Authors: Samel Ulf‐Rainer , Kohler Walter , Gamer Armin Otto , Keuser Ullrich , Yang Shang‐Tian , Jin Ying , Lin Meng , Wang Zhongqiang , Teles Joaquim Henrique
Published: January 2018

The article contains sections titled:1.Introduction2.Physical Properties3.Chemical Properties4.Production4.1.Carbonylation of Ethylene (BASF Process)4.2.Oxidation of Propanal4.3.Direct Oxidation of Hydrocarbons4.4.Production by Fermentation5.Storage and Transportation6.Quality Specifications7.Environmental Protection8.Uses8.1.Use as Food and Feed Preservative8.2.Other Uses9.Economic Aspects10.Toxicology11.Derivatives11.1.Salts11.2.Propionic Anhydride and Propionyl Chloride11.3.Esters11.4.Chloropropionic Acid and Derivatives11.4.1.Properties and Production11.4.1.1.2‐Chloropropionic Acid and Derivatives11.4.1.2.3‐Chloropropionic Acid and Derivatives11.4.1.3.2,2‐Dichloropropionic Acid11.4.2.Uses11.4.2.1.2‐Chloropropionic Acid and Derivatives11.4.2.2.3‐Chloropropionic Acid11.4.2.3.2,2‐Dichloropropionic Acid11.4.3.Toxicology
Placebo‐controlled crossover assessment of mecasermin for the treatment of Rett syndrome
Authors: O'Leary Heather M. , Kaufmann Walter E. , Barnes Katherine V. , Rakesh Kshitiz , Kapur Kush , Tarquinio Daniel C. , Cantwell Nicole G. , Roche Katherine J. , Rose Suzanne A. , Walco Alexandra C. , Bruck Natalie M. , Bazin Grace A. , Holm Ingrid A. , Alexander Mark E. , Swanson Lindsay C. , Baczewski Lauren M. , Mayor Torres Juan M. , Nelson Charles A. , Sahin Mustafa
Published: January 2018

Objective

To measure the efficacy of mecasermin (recombinant human insulin‐like growth factor 1, rhIGF‐1), for treating symptoms of Rett syndrome (RTT) in a pediatric population using a double‐blind crossover study design.

Methods

Thirty girls with classic RTT in postregression stage were randomly assigned to placebo or rhIGF‐1 in treatment period 1 and crossed over to the opposite assignment for period 2 (both 20 weeks), separated by a 28‐week washout period. The primary endpoints were as follows: Anxiety Depression and Mood Scale (ADAMS) Social Avoidance subscale, Rett Syndrome Behaviour Questionnaire (RSBQ) Fear/Anxiety subscale, Parent Target Symptom Visual Analog Scale (PTSVAS) top three concerns, Clinical Global Impression (CGI), Parent Global Impression (PGI), and the Kerr severity scale. Cardiorespiratory‐ and electroencephalography (EEG)‐based biomarkers were also analyzed.

Results

There were no significant differences between randomization groups. The majority of AEs were mild to moderate, although 12 episodes of serious AEs occurred. The Kerr severity scale, ADAMS Depressed Mood subscale, Visual Analog Scale Hyperventilation, and delta average power change scores significantly increased, implying worsening of symptoms. Electroencephalography (EEG) parameters also deteriorated. A secondary analysis of subjects who were not involved in a placebo recall confirmed most of these findings. However, it also revealed improvements on a measure of stereotypic behavior and another of social communication.

Interpretation

As in the phase 1 trial, rhIGF‐1 was safe; however, the drug did not reveal significant improvement, and some parameters worsened.
Strengthening Effect and Texture of Mg–3Li Alloys Strengthened by Various Rare‐Earth Elements
Authors: Bao Lei , Le Qichi , Zhang Zhiqiang
Published: January 2018

Three Mg–3Li–0.4Zr alloys strengthened by various rare‐earth elements (RE: Gd, Nd, and Ce) are prepared and studied to obtain the strengthening effect and texture. The results indicate that Gd exhibits a dramatic strength enhancement with minimum ductility decrease compared with Nd and Ce, which is primarily attributed to the effective pinning effect by the solid dissolved Gd atoms and a great amount of dispersing and homogeneously distributing precipitates with the size from nanometers to decades of nanometers. Moreover, the grain boundary segregated Gd is able to restrain the movement of grain boundaries, which is also the primary strengthening mechanism of Nd and Ce elements. Aging treatment shows improvement on mechanical properties of the three RE‐containing alloys, but with little obvious effect. At last, Gd‐containing Mg–3Li–0.4Zr alloy has good application potential as a kind of new superlight structural material. Pyramidal  slip and tension twinning are the primary mechanisms in the early stage of the extrusion process. Basal  slip becomes the primary mechanism accompanied by the transfer of texture from extrusion texture to RE‐texture ( parallel to extrusion direction) when the complete dynamic recrystallization is achieved.
Integration of Phase‐Change Materials with Electrospun Fibers for Promoting Neurite Outgrowth under Controlled Release
Authors: Xue Jiajia , Zhu Chunlei , Li Jianhua , Li Haoxuan , Xia Younan
Published: January 2018

A temperature‐regulated system for the controlled release of nerve growth factor (NGF) to promote neurite outgrowth is reported. The system is based upon microparticles fabricated using coaxial electrospray, with the outer solution containing a phase‐change material (PCM) and the inner solution encompassing payload(s). When the temperature is kept below the melting point of the PCM, there is no release due to the extremely slow diffusion through a solid matrix. Upon increasing the temperature to slightly pass the melting point, the encapsulated payload(s) can be readily released from the melted PCM. By leveraging the reversibility of the phase transition, the payload(s) can be released in a pulsatile mode through on/off heating cycles. The controlled release system is evaluated for potential use in neural tissue engineering by sandwiching the microparticles, coloaded with NGF and a near‐infrared dye, between two layers of electrospun fibers to form a trilayer construct. Upon photothermal heating with a near‐infrared laser, the NGF is released with well‐preserved bioactivity to promote neurite outgrowth. By choosing different combinations of PCM, biological effector, and scaffolding material, this controlled release system can be applied to a wide variety of biomedical applications.
Programmable Light‐Activated Gradient Materials Based on Graphene–Polymer Composites
Authors: Zhang Yuanyuan , Tan Mei Chee
Published: January 2018

Recently, adaptive programmable materials capable of changing their shape to perform complex motions in response to an external stimulus have attracted tremendous interest. The shape‐changing abilities rely heavily on the non‐linear response of a localized area, where generally an external stimulus would cause distortion due to non‐uniform volumetric changes. Hence, creating materials with heterogeneous compositions and structures have become an effective strategy to achieve the non‐uniform volumetric changes. Here, a versatile strategy that harnesses the concepts of structural and compositional gradients to guide the design of programmable light‐activated materials with continuous changing structures and their correspondingly responsive behavior are developed. These materials compose of a bilayer structure including ultraviolet‐cured Norland Optical Adhesive (NOA) 73 support layer and a structural and compositional gradient layer of polyethylenimine (PEI)‐modified graphene oxide (GO) complexes. The volumetric mismatch between these two layers leads to the reversible three‐dimensional deformation of PEI‐GO/NOA 73 bilayers. The PEI density and the extent of GO reduction lead to different light‐sensing abilities, which result in different extent of deformation and deformation/reversal speed. By controlling the composition of each PEI‐GO segment, programmable light‐activated actuations, such as helical buckling with varying pitch‐sizes of a gradient‐based PEI‐GO/NOA 73 actuator are demonstrated.
Platinum‐Palladium Core–Shell Nanoflower Catalyst with Improved Activity and Excellent Durability for the Oxygen Reduction Reaction
Authors: Jauhar Altamash M. , Hassan Fathy M. , Cano Zachary P. , Hoque Md Ariful , Chen Zhongwei
Published: January 2018

In this work, highly active and stable platinum–palladium core–shell nanoflowers supported on sulfur‐doped graphene (PtPd‐NF/SG) with a polyol reduction method are synthesized. Platinum is decorated on palladium seeds to form core–shell structured floral petals to improve surface activity and give high electrochemically active surface area and stability. The catalyst is deposited on sulfur‐doped graphene to induce highly favorable catalyst‐support interactions to ensure long‐term electrochemical stability. The specific activity and mass activity of the synthesized core–shell nanocatalysts are 3.2 and 4.7 times higher than commercial Pt/C toward oxygen reduction reaction, respectively. After 10 000 testing cycles, the mass and specific activity of the catalyst is ≈25 and ≈18 times higher than the Pt/C benchmark catalyst, respectively. The enhanced electrochemical activity and excellent stability of PtPd‐NF/SG can be attributed to the 2D core–shell nanoflower structure, weak binding of hydroxyl groups to the platinum metal deposited on palladium, and robust sulfur‐doped graphene support.
A Redox‐Active Electrochemical Decoder
Authors: Gaikwad Pramod , Misal Mahavir , Khaire Siddhi , Raafik Abdul , Aralekallu Shambhulinga , Varhade Swapnil , Bhat Zahid Manzoor , Kottaichamy Alagar Raja , Devendrachari Mruthyunjayachari Chattanahalli , Gautam Manu , Thotiyl Musthafa Ottakam
Published: January 2018

In communication systems, transmission of data between different locations requires encoders for encryption and decoders for decrypting encoded data. In modern digital devices, these functions are performed by transistors from their distinct logic levels. It is demonstrated that a redox‐active interface with twin interfacial states can decrypt encoded information through electrochemical means; consequently, it can function as an electrochemical decoder in memory devices. The redox‐active half‐cell electrode/electrolyte interface of the device furnishes bistable conducting and nonconducting states providing the logic HIGH and logic LOW levels of operation, respectively. The logic HIGH level of operation is prompted by self‐charge injection into the redox‐active polymeric backbone which is confirmed by quartz crystal microbalance, galvanostatic intermittent titration technique, and spectroelectrochemistry. A single cathodic interface allows bistable interfacial chemistry; consequently, ‘n’ cell combination can process second possibilities demonstrating the power of electrochemical interface in decoding encoded information.
Cobalt(II) Porphyrin Catalyzed Cascade Reaction of Pyrrolyl Ketones for Construction of Polysubstituted Pyrrolizidines and Pyrrolizines
Authors: Hao Fei , Reddy Annapureddy Rajasekar , Zhou Cong‐Ying , Che Chi‐Ming
Published: January 2018

We developed an efficient method for the synthesis of polysubstituted 3H‐pyrrolizines and pyrrolizidines via a cobalt(II) porphyrin catalyzed intramolecular cyclopropanation/ring opening cascade reaction of hydrazones derived from pyrrolyl ketones. With CoII(F20TPP) as catalyst, a variety of pyrrolyl ketones underwent condensation, intramolecular cyclopropanation/ring opening cascade reaction and subsequent oxidation or reduction to give 3H‐pyrrolizines or pyrrolizidines in good yields. This Co(II) catalyzed cascade reaction provides a rapid access to polysubstituted 3H‐pyrrolizines and pyrrolizidines from readily accessible starting materials.

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Nonspiro, Fluorene‐Based, Amorphous Hole Transporting Materials for Efficient and Stable Perovskite Solar Cells
Authors: Daškevičiū tė Šarūnė , Sakai Nobuya , Franckevičius Marius , Daškevičienė Marytė , Magomedov Artiom , Jankauskas Vygintas , Snaith Henry J. , Getautis Vytautas
Published: January 2018

Novel nonspiro, fluorene‐based, small‐molecule hole transporting materials (HTMs) V1050 and V1061 are designed and synthesized using a facile three‐step synthetic route. The synthesized compounds exhibit amorphous nature with a high glass transition temperature, a good solubility, and decent thermal stability. The planar perovskite solar cells (PSCs) employing V1050 generated an excellent power conversion efficiency of 18.3%, which is comparable to 18.9% obtained with the state‐of‐the‐art Spiro‐OMeTAD. Importantly, the devices based on V1050 and V1061 show better stability compared to devices based on Spiro‐OMeTAD when aged without any encapsulation under uncontrolled humidity conditions (relative humidity around 60%) in the dark and under continuous full sun illumination.
Ultrathin Organic Solar Cells with a Power Conversion Efficiency of Over ≈13.0%, Based on the Spatial Corrugation of the Metal Electrode–Cathode Fabry–Perot Cavity
Authors: In Sungjun , Park Namkyoo
Published: January 2018

The application of nanophotonic structures for organic solar cells (OSCs) is quite popular and successful, and has led to increased optical absorption, better spectral overlap with solar irradiances, and improved charge collection. Significant improvements in the power conversion efficiency (PCE) have also been reported, exceeding 11%. Nonetheless, with the given material properties of OSCs with low optical absorption, narrow spectrum, short transport length of carriers, and nonuniform photocarrier generations resulting from the nanophotonic structure, the PCE of single‐junction OSCs has been stagnant over the past few years, at a barrier of 12%. Here, an ultrathin inverted OSC structure with the highest efficiency of ≈13.0%, while being made from widely used organic materials, is demonstrated. By introducing a smooth spatial corrugation to the vertical plasmonic cavity enclosing the active layer, in‐plane propagation modes and hybridized Fabry–Perot cavity modes inside the corrugated cavity are derived to achieve an ultralow Q, uniform coverage of optical absorption, in addition to uniform photocarrier generation and transport. As the first demonstration of ultra‐broadband absorption with the introduction of spatial corrugation to the ultrathin metal film electrode–cathode Fabry–Perot cavity, future applications of the same concept in other light‐harvesting devices utilizing different materials and structures are expected.
La2/3Sr1/3VO3 Thin Films: A New p‐Type Transparent Conducting Oxide with Very High Figure of Merit
Authors: Hu Ling , Wei Renhuai , Yan Jian , Wang Dong , Tang Xianwu , Luo Xuan , Song Wenhai , Dai Jianmin , Zhu Xuebin , Zhang Changjin , Sun Yuping
Published: January 2018

Transparent conducting oxides (TCOs) are a unique series of materials combining electrical conductivity with optical transparency. Most of the commercially available TCOs are of the n‐type. The performance of p‐type TCOs, however, is far behind their n‐type TCO counterparts primarily due to the doping bottleneck and low hole mobility. Herein, a Mott–Hubbard insulator of LaVO3 is proposed as the starting point for exploring p‐type TCOs. Substitution of La3+ by Sr2+ can introduce high hole carrier concentration at the top of the valence band to overcome the doping bottleneck. Combining a modest carrier mobility with weak absorption in the visible region, La1‐xSrxVO3 compounds can serve as new p‐type TCOs and exhibit good balance of the tradeoffs between electrical conductivity and optical transparency. It is demonstrated that La2/3Sr1/3VO3 thin films exhibit a high conductivity of 742.3–872.3 S cm−1 at room temperature and a high transmission of 53.9–70.1% in the visible region, which leads to the highest figure of merit among p‐type TCOs so far.
Extending the phenotype associated with the CSNK2A1‐related Okur–Chung syndrome—A clinical study of 11 individuals
Authors: Owen Ceris I. , Bowden Ramsay , Parker Michael J. , Patterson Jo , Patterson Joan , Price Sue , Sarkar Ajoy , Castle Bruce , Deshpande Charulatha , Splitt Miranda , Ghali Neeti , Dean John , Green Andrew J. , Crosby Charlene ,   Deciphering Developmental Disorders Study, Tatton‐Brown Katrina
Published: January 2018

Variants in the Protein Kinase CK2 alpha subunit, encoding the CSNK2A1 gene, have previously been reported in children with an intellectual disability and dysmorphic facial features syndrome: now termed the Okur–Chung neurodevelopmental syndrome. More recently, through trio‐based exome sequencing undertaken by the Deciphering Developmental Disorders Study (DDD study), a further 11 children with de novo CSNK2A1 variants have been identified. We have undertaken detailed phenotyping of these patients. Consistent with previously reported patients, patients in this series had apparent intellectual disability, swallowing difficulties, and hypotonia. While there are some shared facial characteristics, the gestalt is neither consistent nor readily recognized. Congenital heart abnormalities were identified in nearly 30% of the patients, representing a newly recognized CSNK2A1 clinical association. Based upon the clinical findings from this study and the previously reported patients, we suggest an initial approach to the management of patients with this recently described intellectual disability syndrome.
Decoupling Hydrogen and Oxygen Production in Acidic Water Electrolysis Using a Polytriphenylamine‐Based Battery Electrode
Authors: Ma Yuanyuan , Dong Xiaoli , Wang Yonggang , Xia Yongyao
Published: January 2018

Hydrogen production through water splitting is considered a promising approach for solar energy harvesting. However, the variable and intermittent nature of solar energy and the co‐production of H2 and O2 significantly reduce the flexibility of this approach, increasing the costs of its use in practical applications. Herein, using the reversible n‐type doping/de‐doping reaction of the solid‐state polytriphenylamine‐based battery electrode, we decouple the H2 and O2 production in acid water electrolysis. In this architecture, the H2 and O2 production occur at different times, which eliminates the issue of gas mixing and adapts to the variable and intermittent nature of solar energy, facilitating the conversion of solar energy to hydrogen (STH). Furthermore, for the first time, we demonstrate a membrane‐free solar water splitting through commercial photovoltaics and the decoupled acid water electrolysis, which potentially paves the way for a new approach for solar water splitting.
Total Synthesis and Stereochemical Revision of Iriomoteolide‐2a
Authors: Sakamoto Keita , Hakamata Akihiro , Tsuda Masashi , Fuwa Haruhiko
Published: January 2018

Total syntheses of the proposed and correct structures of iriomoteolide‐2a, a cytotoxic marine macrolide natural product with an unusual 23‐membered macrolactone skeleton, have been accomplished for the first time. The synthesis of the correct structure involves an asymmetric epoxidation/diepoxide cyclization cascade for the construction of the bis(tetrahydrofuran) moiety, a Suzuki–Miyaura coupling for the fragment assembly, and a ring‐closing metathesis for the closure of the macrocyclic backbone. In addition, the original stereochemical assignment of iriomoteolide‐2a was revised.
Evolution of surface functional groups of coal char during coal combustion under O2/CO2 atmospheres
Authors: Yan Dawei , Gu Mingyan , Lin Yuyu , Chen Ping , He Xianhui
Published: January 2018

In this study, quantitative analysis was conducted to study the changes in characteristics of surface functional groups of coal char under O2/CO2 atmospheres using Fourier transform infrared analysis. A drop tube furnace was explored. Besides, the effect of the oxygen‐containing functional group on the generation characteristics of NO emission was also investigated. The results showed that CH2/CH3 is highly influenced by the process and atmosphere of coal combustion. The burning of coal increases the contents of aromatic hydrogen and aromaticity on the surface of coal char particles, and it decreases the content of lipid hydrogen. The oxygen concentration exhibits a significant effect on the oxygen‐containing functional groups in coal char, which promotes the reduction reaction of NO. There is an optimum oxygen concentration of 30% that creates the best NO reduction effect caused by the oxygen‐containing functional groups.
Advanced architectures in the design of responsive polymers for cancer nanomedicine
Authors: Wagner Angela M. , Spencer David S. , Peppas Nicholas A.
Published: January 2018

In recent decades, nanoparticles have shown significant promise as an oncology treatment modality. Responsive polymers represent a promising class of nanoparticles that can trigger delivery through the exploitation of a specific stimuli. Response to a stimulus is one of the most basic processes found in living systems. As such, the desire to engineer dynamic and functional materials is becoming more prevalent in an effort to achieve precise control over our environment. The combination of controlled radical polymerization and high yielding chemistry strategies provide an excellent basis for the development of the next generation of drug delivery systems. The versatility of polymer chemistries available enables the synthesis of increasingly complex architectures with enhanced delivery specificity and control over the desired properties to interface with biological systems. This tutorial review highlights recent developments in polymer‐based approaches to internally responsive nanoparticles for oncology. Presented are concise overviews of the current challenges and opportunities in cancer nanomedicine, common polymer‐based architectures, and the basis for internally triggered stimuli–response relationships commonly employed in oncology applications. Examples of the chemistry used in the design of environmentally labile nanomaterials are discussed, and we outline recent advances in creating advanced bioresponsive drug delivery architectures. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46154.
Synthesis of a polymeric sensor containing an occluded pyrylium salt and its application in the colorimetric detection of trimethylamine vapors
Authors: Bustamante Fonseca Saúl E. , Rivas Bernabé L. , García Pérez José M. , Vallejos Calzada Saúl , García Félix
Published: January 2018

A dense membrane (MS) based on vinyl polymers and containing a pyrylium salt [2,6‐diphenyl‐4(p‐methacryloyloxy)phenylpyryliumtetrafluoroborate] was prepared. The MS has hydrophilic and sensory properties that make it a good material for the selective colorimetric detection of trimethylamine (TMA) vapors, a biogenic amine of great importance in food safety. The polymeric sensor changes from yellow to an intense pink color with increasing concentrations of TMA. The material could be reused in the presence of HCl vapors for at least 10 times. The detection and quantification limits were determined by ultraviolet–visible absorption spectroscopy (4.42 and 13.40 ppm, respectively) and by the RGB parameters of digital color (3.37 and10.22 ppm, respectively). © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46185.
Synthesis of high‐solid‐content, acrylic pressure‐sensitive adhesives by solvent polymerization
Authors: Kuo Chung‐Feng Jeffrey , Chen Jiong‐Bo
Published: January 2018

In this study, we prepared high solid content (SC), solvent‐based, acrylic pressure‐sensitive adhesives (PSAs) with n‐dodecyl mercaptan as a chain‐transfer agent (CTA) and studied the crosslinking reactions between the crosslinker and the acrylic PSAs. Acrylic PSAs were prepared from 2‐ethyl hexyl acrylate, acrylic acid (AA), and 2‐azobisisobutyronitrile with a solution polymerization process. The results show AA resulted in an effective molecular weight in the acrylic PSAs, as it improved the hydrophilicity with increasing peel strength of the acrylic PSAs. As for the high SC, the molecular weight and system viscosity decreased through the addition of CTA. At a constant AA amount, the addition of CTA decreased the molecular weight and increased the hydrophobicity of the acrylic PSAs; this decreased the peel strength of the acrylic PSAs on the glass. Furthermore, the addition of CTA decreased the molecular weight and improved the acrylic PSAs' surface morphologies and optical properties. The acrylic PSAs produced in this study could meet production needs. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46257.
Tuning of Thermoresponsivity of a Poly(2‐alkyl‐2‐oxazoline) Block Copolymer by Interaction with Surface‐Active and Chaotropic Metallacarborane Anion
Authors: Ďorďovič Vladimír , Verbraeken Bart , Hogenboom Richard , Kereïche Sami , Matějíček Pavel , Uchman Mariusz
Published: January 2018

Thermoresponsive nanoparticles based on the interaction of metallacarboranes, bulky chaotropic and surface‐active anions, and poly(2‐alkyl‐2‐oxazoline) block copolymers were prepared. Recently, the great potential of metallacarboranes have been recognized in biomedicine and many delivery nanosystems have been proposed. However, none of them are thermoresponsive. Therefore, a thermoresponsive block copolymer, poly(2‐methyl‐2‐oxazoline)‐block‐poly(2‐n‐propyl‐2‐oxazoline) (PMeOx–PPrOx), was synthesized to encapsulate metallacarboranes. Light scattering, NMR spectroscopy, isothermal titration calorimetry, and cryogenic TEM were used to characterize all solutions of the formed nanoparticles. The cloud‐point temperature (TCP) of the block copolymer was observed at 30 °C and polymeric micelles formed above this temperature. Cobalt bis(dicarbollide) anion (COSAN) interacts with both polymeric segments. Depending on the COSAN concentration, this affinity influenced the phase transition of the thermoresponsive PPrOx block. The TCP shifted to lower values at a lower COSAN content. At higher COSAN concentrations, the hybrid nanoparticles are fragmented into relatively small pieces. This system is also thermoresponsive, whereby an increase in temperature leads to higher polymer mobility and COSAN release.
A Spin‐Active, Electrochromic, Solvent‐Free Molecular Liquid Based on Double‐Decker Lutetium Phthalocyanine Bearing Long Branched Alkyl Chains
Authors: Zielinska Agnieszka , Takai Atsuro , Sakurai Hiroya , Saeki Akinori , Leonowicz Marcin , Nakanishi Takashi
Published: January 2018

Synthesis and characterization of a novel, multifunctional, solvent‐free room‐temperature liquid based on alkylated double‐decker lutetium(III) phthalocyanine (Pc2Lu) are described. Lowering of the melting point and viscosity of intrinsically solid Pc2Lu compounds has been achieved through the attachment of flexible, bulky, and long branched‐alkyl chains, that is, thio‐2‐octyldodecyl, to the periphery of the Pc2Lu unit. The embedded Pc2Lu unit maintains its inherent molecular functions, such as spin‐active nature and electrochromic behavior in the liquid state. Comparison of the properties with a solid‐like Pc2Lu derivative, functionalized with shorter alkyl chains, that is, thio‐2‐ethylhexyl, underlines the importance of the hampering effect on the π–π interactions of neighboring Pc2Lu molecules by bulkier and longer branched‐alkyl chains. This study could possibly pave the way for novel multifunctional liquids whose spin‐activities are associated with their rheological or optoelectronic properties.
Application of hydrocarbon and perfluorocarbon oxygen vectors to enhance heterologous production of hyaluronic acid in engineered Bacillus subtilis
Authors: Westbrook Adam W. , Ren Xiang , Moo‐Young Murray , Chou C. Perry
Published: January 2018

In microbial cultivations for hyaluronic acid (HA) production, oxygen can be a limiting substrate due to its poor solubility in aqueous medium and the substantial increase in culture viscosity at relatively low HA titers. Shear stress due to the high agitation and aeration rates required to overcome oxygen limitation may reduce the quality (i.e., molecular weight) of HA, and production costs associated with power consumption and supplemental oxygen may be excessive. Here, we report the application of oxygen vectors to the heterologous production of HA in engineered Bacillus subtilis, leading to significantly improved culture performance. We first derived an improved HA‐producing strain of B. subtilis through engineering of the promoter driving coexpression of seHas and tuaD, leading to high‐level HA production. Out of seven potential oxygen vectors evaluated in a preliminary screening, significant improvements to the HA titer and/or cell density were observed in cultures containing n‐heptane, n‐hexadecane, perfluoromethyldecalin, and perfluoro‐1,3‐dimethylcyclohexane. Adjustments to the vector concentration, timing of vector addition, and the agitation rate resulted in further enhancements, with the HA titer reaching up to 4.5 g/L after only 10 hr cultivation. Moreover, our results indicate that certain vectors may alter the functional expression of Class I hyaluronan synthase (HAS) in B. subtilis, and that higher shear rates may drive more carbon flux through the HA biosynthetic pathway without negatively affecting the MW. Our study demonstrates the efficacy of oxygen vectors to enhance heterologous HA production in B. subtilis, and provides valuable insight for future bioprocess development in microbial HA production.
The Control of Transition Behavior of VO2 Film Deposited on Sapphire (0001) Substrate by the Organic Polymer‐Assisted Thermal Deposition
Authors: Lee Myeongsoon , Kim Don
Published: January 2018

We present the effects of organic additives (sucrose, polyvinylalcohol [PVA], and polyvinylpyrrolidone [PVP]) on a precursor solution (VO2+ ion) to the physicochemical properties of the thermally deposited VO2 film on sapphire (0001) plane. All the VO2 films, which deposited with assistance of the organic chemicals, showed a sudden change in resistance measurement near 340 K, but the sudden change did not appear in the film which deposited without the organic additives. The X‐ray diffractometer patterns of the films show monoclinic type VO2 (M‐VO2) as main phase, which has preferred growing axis (020) and (−211), and V2O5 as impurity phase. The intensity of the impurity peaks was minimized in PVP‐assisted deposition and showed the best performance as a smart window, ~10% transmittance gap between low and high temperature phases at 1550 nm. The atomic ratio of oxygen/carbon in the organic additives (1:1 in sucrose –[CH2O]n–, 1:2 in PVA –[C2H4O]n–, and 1:6 in PVP –[C6H9NO]n–) seems an important condition to determine the performance of the smart window.
The characteristics of cognitive impairment in subjective chronic tinnitus
Authors: Wang Yi , Zhang Jian‐Ning , Hu Wei , Li Ji‐Jun , Zhou Jia‐Xuan , Zhang Jian‐Ping , Shi Guo‐Feng , He Ping , Li Zai‐Wang , Li Ming
Published: January 2018

Introduction

Subjective chronic tinnitus is a common medical syndrome with a high frequency of cognitive impairment; however, the characteristics of cognitive impairment in chronic tinnitus are poorly understood. Investigating the scope of cognitive impairment across the severity spectrum of tinnitus patients may shed light on the issue.

Methods

A consecutive series of 207 subjective chronic tinnitus patients were classified into mild tinnitus group (n = 95) and severe tinnitus group (n = 112) by THI score (the cutoff THI scores were 37/38). These patients were assessed using the Cognitive Abilities Screening Instrument (CASI) and P300 event‐related potential.

Results

Although pure tone averages were not different between mild or severe tinnitus patients, severe tinnitus patients scored lower on the CASI assessment as well as almost all subdomains of CASI, particularly in items such as “short‐term memory,” “concentration or mental manipulation,” “orientation,” “abstraction and judgment,” “language abilities,” and “visual construction.” Furthermore, compared to mild tinnitus patients, severe tinnitus patients exhibited longer N2 and P3 latencies. Finally, a correlation analysis revealed that tinnitus severity was negatively correlated with CASI score and positively correlated with N2 and P3 latencies.

Conclusions

This study reveals that tinnitus patients on the severe end of the spectrum may be at risk for serious cognitive deficits, which may not be a secondary response to disease manifestations but a primary feature of the underlying disease.
Object‐oriented modeling approach of universal education software
Authors: Petković Dalibor , Jovic Srdjan , Golubovic Zoran
Published: January 2018

Since learning process could be very challenging task for scholars in this article an attempt to analyze and model a universal education software (UES) was made. The software was modeled from beginning of the life cycle by object‐orientated modeling approach. In order to visually represent any research problem unified modeling language is the most appropriate and efficient tool. In this paper UES was modeled by unified modeling language diagrams which could lead to better development and understanding of the behavior and structure of the software. Modeling by unified modeling language is a new way of thinking about systems and the development process which involved object modeling. The main concept of the object modeling is the object identification within the system environment, and the relationships and interactions between the objects.
Spoon nails: still seen in today's world
Authors: Moiz Bushra
Published: January 2018

Key Clinical Message

Koilonychia is a nail abnormality characterized by thin, brittle, and spoon‐shaped nails. It is frequently observed in chronic iron deficiency secondary to malnutrition, chronic blood loss, or malabsorption. It may also be idiopathic or related to occupation and rare systemic disorders. Presence of koilonychia should prompt investigations for iron deficiency.
Interfacial Generation of a Carbanion: The Key Step of PTC Reaction Directly Observed by Second Harmonic Generation
Authors: Hamkalo Michal , Fita Piotr , Fedorynski Michal , Makosza Mieczyslaw
Published: January 2018

We present the first unambiguous evidence of the interfacial mechanism of phase‐transfer catalysis (PTC) by direct observation of the formation of carbanions in the interfacial region between the aqueous and the organic phase by using a surface‐sensitive spectroscopic method known as second harmonic generation (SHG). Ion exchange of carbanions adsorbed at the surface after addition of lipophilic tetraalkylammonium salts (TAA) to organic phase and transport of the lipophilic ion‐pairs to the organic phase is observed. Results allow for the formulation of a more detailed mechanism of PTC.
Phenylene Bridged Cyclic Azaacenes: Dimers and Trimers
Authors: Hahn Sebastian , Koser Silke , Hodecker Manuel , Seete Pascal , Rominger Frank , Miljanić Ognjen Š. , Dreuw Andreas , Bunz Uwe H. F.
Published: January 2018

The synthesis and characterization of novel macrocyclic, phenylene‐bridged azaacenes is reported. These species were obtained either by a conventional benzoin– diamine condensation, as shown for the case of the cyclotrimers, in which the azaacene units are separated by meta‐connected phenylene bridges, or by a Buchwald–Hartwig‐type Pd‐catalyzed coupling, which employs 1,2,5,6‐tetrabromodibenzocyclooctatetraene as the substrate and bis‐TIPS‐ethynylated diaminobenzene, ‐naphthalene or ‐anthracene as the coupling partner to give the double coupling products azaacene‐annulated dibenzocyclooctatetraenes in moderate yields. The macrocycles show strong emission and light emitting diodes have been built with brightnesses exceeding 1600 cd m−2. We evaluated the optical and electronic properties and the solid‐state structures of the molecules and discuss their properties through comparison with their linear and tetrameric N‐heteroacene counterparts.
Single Ion Magnets from 3d to 5f: Developments and Strategies
Authors: Feng Min , Tong Ming‐Liang
Published: January 2018

Single‐ion magnets (SIMs), exhibiting slow magnetization relaxation in the absence of the magnetic field, originate from their single spin‐carrier centre. In pursuit of high‐performance magnetic properties, such as high spin‐reversal barrier and high blocking temperature, various metal centres were investigated to establish SIMs, including 3d and 5d transition metal ions, 4f lanthanide ions, and 5f actinide ions, which possess unique zero‐field splitting and magnetic properties. Therefore, proper ligand field is of great importance to different types of metals. In the given great breakthroughs since the first SIM, [Pc2Tb]− (Pc=dianion of phthalocyanine), was reported, strategies of ligand field design have emerged. In this review, the developments of SIMs with different metal centres are summarized, as well as the possible strategies.
A Three‐State System Based on Branched DNA Hybrids
Authors: He Shiliang , Richert Clemens
Published: January 2018

There is a need for materials that respond to chemical or physical stimuli through a change in their structure. While a transition between water‐soluble form and solid is not uncommon for DNA‐based structures, systems that transition between three different states at room temperature and ambient pressure are rare. Here we report the preparation of branched DNA hybrids with eight oligodeoxycytidylate arms via solution‐phase, H‐phosphonate‐based synthesis. Some hybrids assemble into hydrogels upon lowering the pH, acting as efficient gelators at pH 4–6, but can also transition into a more condensed solid state form upon exposure to divalent cations. Together with the homogeneous solutions that the i‐motif‐forming compounds give at neutral pH, three‐state systems result. Each state has its own color, if chromophores are included in the system. The assembly and gelation properties can be tuned by choosing the chain length of the arms. Their responsive properties make the dC‐rich DNA hybrids candidates for smart material applications.
Computational Study of the Aza‐Michael Addition of the Flavonoid (+)‐Taxifolin in the Inhibition of β‐Amyloid Fibril Aggregation
Authors: Ginex Tiziana , Trius Marta , Luque F. Javier
Published: January 2018

Inhibition of abnormal protein self‐aggregation is an attractive strategy against amyloidogenic diseases, but has found limited success due to the complexity of protein self‐assembly, the absence of fully reproducible aggregation assays, and the scarce knowledge of the inhibition mechanisms by small molecules. In this context, catechol‐containing compounds may lead to covalent adducts with amyloid fibrils that interfere with the aggregation process. In particular, the covalent adduct formed between the oxidized form of (+)‐taxifolin and an β‐amyloid (Aβ42) suggests the involvement of a specific recognition motif that enables the chemical reaction with Aβ42. In this study, we have examined the mechanisms implicated in the aza‐Michael addition of the o‐quinone species of (+)‐taxifolin with Aβ42 fibrils. The results support the binding of (+)‐taxifolin to the hydrophobic groove delimited by the edges defined by Lys16 and Glu22 residues in the fibril. The chemical reaction proceeds through the nucleophilic attack of the deprotonated amino group of a Lys16 residue in a process activated by the interaction between the o‐quinone ring with a vicinal Lys16 residue, as well as by a water‐assisted proton transfer, which is the rate‐limiting step of the reaction. This specific inhibition mechanism, which may explain the enhanced anti‐aggregating activity of oxidized flavonoids compared to fresh compounds, holds promise for developing disease‐modifying therapies.