bluuebunny/crossref_metadata_2025_split huggingface dataset:
Synergy of Ionic and Dipolar Effects by Molecular Design for pH Sensing beyond the Nernstian Limit
Authors: Tseng Chiao‐Wei , Wen Chenyu , Huang Ding‐Chi , Lai Chin‐Hung , Chen Si , Hu Qitao , Chen Xi , Xu Xingxing , Zhang Shi‐Li , Tao Yu‐Tai , Zhang Zhen 
Published: November 2019

AbstractKnowledge of interfacial interactions between analytes and functionalized sensor surfaces, from where the signal originates, is key to the development and application of electronic sensors. The present work explores the tunability of pH sensitivity by the synergy of surface charge and molecular dipole moment induced by interfacial proton interactions. This synergy is demonstrated on a silicon‐nanoribbon field‐effect transistor (SiNR‐FET) by functionalizing the sensor surface with properly designed chromophore molecules. The chromophore molecules can interact with protons and lead to appreciable changes in interface dipole moment as well as in surface charge state. In addition, the dipole moment can be tuned not only by the substituent on the chromophore but also by the anion in the electrolyte interacting with the protonated chromophore. By designing surface molecules to enhance the surface dipole moment upon protonation, an above‐Nernstian pH sensitivity is achieved on the SiNR‐FET sensor. This finding may bring an innovative strategy for tailoring the sensitivity of the SiNR‐FET‐based pH sensor toward a wide range of applications.
Progress and Challenges Toward the Rational Design of Oxygen Electrocatalysts Based on a Descriptor Approach
Authors: Liu Jieyu , Liu Hui , Chen Haijun , Du Xiwen , Zhang Bin , Hong Zhanglian , Sun Shuhui , Wang Weichao 
Published: November 2019

AbstractOxygen redox catalysis, including the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), is crucial in determining the electrochemical performance of energy conversion and storage devices such as fuel cells, metal–air batteries,and electrolyzers. The rational design of electrochemical catalysts replaces the traditional trial‐and‐error methods and thus promotes the R&D process. Identifying descriptors that link structure and activity as well as selectivity of catalysts is the key for rational design. In the past few decades, two types of descriptors including bulk‐ and surface‐based have been developed to probe the structure–property relationships. Correlating the current descriptors to one another will promote the understanding of the underlying physics and chemistry, triggering further development of more universal descriptors for the future design of electrocatalysts. Herein, the current benchmark activity descriptors for oxygen electrocatalysis as well as their applications are reviewed. Particular attention is paid to circumventing the scaling relationship of oxygen‐containing intermediates. For hybrid materials, multiple descriptors will show stronger predictive power by considering more factors such as interface reconstruction, confinement effect, multisite adsorption, etc. Machine learning and high‐throughput simulations can thus be crucial in assisting the discovery of new multiple descriptors and reaction mechanisms.
Transient Electronic Depletion and Lattice Expansion Induced Ultrafast Bandedge Plasmons
Authors: Zhang Xinping , Wang Meng , Tang Fawei , Zhang Huanzhen , Fu Yulan , Liu Dong , Song Xiaoyan 
Published: November 2019

AbstractStrong optical excitation of plasmonic nanostructures may induce simultaneous interband and intraband electronic transitions. However, interaction mechanisms between interband, intraband, and plasmon‐band processes have not been thoroughly understood. In particular, optical‐heating‐induced lattice expansion, which definitely leads to shift of the Fermi level, has not been taken into account in plasmonic studies. Here, it is shown that plasmonic bandedge shift is responsible for the optical modulation on the boundary between plasmonic electron oscillation and interband transitions via investigations on gold nanofilms and nanoparticles. Strong optical excitation induces transient depletion of the conduction band just below the Fermi level through intraband transitions, while the subsequent lattice heating induces transient thermal expansion and hence lowers the Fermi level. Both effects reduce the threshold for interband transitions and therefore push the plasmonic bandedge to the red. These discoveries introduce a first correlation between plasmonic response and optical excitation induced thermal expansion of lattices. The revealed Fermi‐level adjustment mechanism allows alignment of electronic levels at the metal–semiconductor interfaces, which applies to all conductive materials and renders reliable physics for the design of plasmonic or optoelectronic devices.
Artificial Inclusion Bodies for Clinical Development
Authors: Sánchez Julieta M. , López‐Laguna Hèctor , Álamo Patricia , Serna Naroa , Sánchez‐Chardi Alejandro , Nolan Verónica , Cano‐Garrido Olivia , Casanova Isolda , Unzueta Ugutz , Vazquez Esther , Mangues Ramon , Villaverde Antonio 
Published: November 2019

AbstractBacterial inclusion bodies (IBs) are mechanically stable protein particles in the microscale, which behave as robust, slow‐protein‐releasing amyloids. Upon exposure to cultured cells or upon subcutaneous or intratumor injection, these protein materials secrete functional IB polypeptides, functionally mimicking the endocrine release of peptide hormones from secretory amyloid granules. Being appealing as delivery systems for prolonged protein drug release, the development of IBs toward clinical applications is, however, severely constrained by their bacterial origin and by the undefined and protein‐to‐protein, batch‐to‐batch variable composition. In this context, the de novo fabrication of artificial IBs (ArtIBs) by simple, cell‐free physicochemical methods, using pure components at defined amounts is proposed here. By this, the resulting functional protein microparticles are intriguing, chemically defined biomimetic materials that replicate relevant functionalities of natural IBs, including mammalian cell penetration and local or remote release of functional ArtIB‐forming protein. In default of severe regulatory issues, the concept of ArtIBs is proposed as a novel exploitable category of biomaterials for biotechnological and biomedical applications, resulting from simple fabrication and envisaging soft developmental routes to clinics.
Band Engineering and Majority Carrier Switching in Isostructural Donor–Acceptor Complexes DPTTA‐FXTCNQ Crystals (X = 1, 2, 4)
Authors: Liang Yingying , Qin Yunke , Chen Jie , Xing Weilong , Zou Ye , Sun Yimeng , Xu Wei , Zhu Daoben 
Published: November 2019

AbstractThree isostructural donor–acceptor complexes DPTTA‐FXTCNQ (X = 1, 2, 4) are investigated experimentally and theoretically. By tuning the number of F atoms in the acceptor molecules, the resulting complexes display a continuous down shift of the valence band maximum, conducting band minimum, and optical bandgap. The majority carriers convert from hole (DPTTA‐F1TCNQ), balanced hole, and electron (DPTTA‐F2TCNQ) to electron (DPTTA‐F4TCNQ). This result shows that band engineering can be realized easily in the donor–acceptor complex systems by tuning the electron affinity of the acceptor. The bandgaps of these three complexes vary from 0.31 to 0.41 eV; this narrow bandgap feature is crucial for achieving high thermoelectric performance and the unintentional doping in DPTTA‐F4TCNQ leads to the effective suppression of the bipolar cancelling effect on the Seebeck coefficient and the highest power factor.
Vapor–liquid equilibria of HFC‐161 + HFC‐32 + DMF ternary mixture for low‐grade heat driven absorption refrigeration system
Authors: Xu Yingjie , Mou Yue , Han Xiaohong , Li Yuebing , Xu Liangfeng , Chen Guangming 
Published: November 2019

AbstractTernary mixture of fluoroethane (HFC‐161) + difluoromethane (HFC‐32)  + N,N‐dimethylformamide (DMF) is a promising working fluid for absorption refrigeration system which is an important energy saving technology receiving more and more attention. Investigation on vapor–liquid equilibrium (VLE) is necessary for further study and the application in absorption system of the ternary mixture. Therefore, an experimental system with continuous vapor‐phase circulation is set up, measuring VLE data within temperature range of 283.15 to 323.15 K. The experimental data is correlated with Wilson and NRTL models, and BP‐ANN method, respectively. The calculating data of Wilson model has the largest relative deviation of 5.14% and average relative deviation of 2.65% for vapor pressure, being the best one. The deviation of molar fraction data obtained with BP‐ANN model has the best average relative deviation 3.07%. However, NRTL model provides a smooth predicted surface. The correlated parameters of the three models are given.
Amyotrophic Lateral Sclerosis with Pallidonigroluysian Degeneration: A Clinicopathological Study
Authors: Ito Junko , Shimizu Hiroshi , Ohta Kentaro , Idezuka Jiro , Tanaka Hajime , Kondo Hiroshi , Nakajima Takashi , Takahashi Hitoshi , Akazawa Kohei , Onodera Osamu , Kakita Akiyoshi 
Published: November 2019

ObjectiveThe pallidonigroluysian (PNL) system, the primary component of corticosubcortical circuits, is generally spared in amyotrophic lateral sclerosis (ALS). We evaluated the clinicopathological features of an unusual form of ALS with PNL degeneration (PNLD) and assessed whether ALS with PNLD represents a distinct ALS subtype.MethodsFrom a cohort of 97 autopsied cases of sporadic ALS with phosphorylated 43kDa TAR DNA‐binding protein (TDP‐43) inclusions, we selected those with PNLD and analyzed their clinicopathological features.ResultsEleven cases (11%) that showed PNLD were divided into 2 subtypes depending on the lesion distribution: (1) extensive type (n = 6), showing widespread TDP‐43 pathology and multisystem degeneration, both involving the PNL system; and (2) limited type (n = 5), showing selective PNL and motor system involvement, thus being unclassifiable in terms of Brettschneiderʼs staging or Nishihiraʼs typing of ALS. The limited type showed a younger age at onset and predominant PNLD that accounted for the early development of extrapyramidal signs. The limited type exhibited the heaviest pathology in the subthalamus and external globus pallidus, suggesting that TDP‐43 inclusions propagated via indirect or hyperdirect pathways, unlike ALS without PNLD, where the direct pathway is considered to convey TDP‐43 aggregates from the cerebral cortex to the substantia nigra.InterpretationThe PNL system can be involved in the disease process of ALS, either nonselectively as part of multisystem degeneration, or selectively. ALS with selective involvement of the PNL and motor systems exhibits unique clinicopathological features and TDP‐43 propagation routes, thus representing a distinct subtype of ALS. ANN NEUROL 2020;87:302–312
Dimethyl Dihydroacridines as Photocatalysts in Organocatalyzed Atom Transfer Radical Polymerization of Acrylate Monomers
Authors: Buss Bonnie L. , Lim Chern‐Hooi , Miyake Garret M. 
Published: November 2019

AbstractDevelopment of photocatalysts (PCs) with diverse properties has been essential in the advancement of organocatalyzed atom transfer radical polymerization (O‐ATRP). Dimethyl dihydroacridines are presented here as a new family of organic PCs, for the first time enabling controlled polymerization of challenging acrylate monomers by O‐ATRP. Structure–property relationships for seven PCs are established, demonstrating tunable photochemical and electrochemical properties, and accessing a strongly oxidizing2PC.+intermediate for efficient deactivation. In O‐ATRP, the combination of PC, implementation of continuous‐flow reactors, and promotion of deactivation through addition of LiBr are critical to producing well‐defined acrylate polymers with dispersities as low as 1.12. The utility of this approach is established through demonstration of the oxygen‐tolerance of the system and application to diverse acrylate monomers, including the synthesis of well‐defined di‐ and triblock copolymers.
Remote Perfluoroalkyl Substituents are Key to Living Aqueous Ethylene Polymerization
Authors: Schnitte Manuel , Scholliers Janine S. , Riedmiller Kai , Mecking Stefan 
Published: November 2019

AbstractIn various nickel(II) salicylaldiminato ethylene polymerization catalysts, which are a versatile mechanistic probe for substituent effects, longer perfluoroalkyl groups exert a strong effect on catalytic activities and polymer microstructures compared to the trifluoromethyl group. This effect is accounted for by a reduced electron density on the active sites, and is also supported by electrochemical studies. Thus, β‐hydride elimination, the key step of chain transfer and branching pathways, is disfavored while chain‐growth rates are enhanced. This enhancement occurs to an extent that enables living polymerizations in aqueous systems to afford ultra‐high‐molecular‐weight polyethylene for various chelating salicylaldimine motifs. These findings are mechanistically instructive as well as practically useful for illustrating the potential of perfluoroalkyl groups in catalyst design.
Bioinspired Nitroalkylation for Selective Protein Modification and Peptide Stapling
Authors: Mahesh Sriram , Adebomi Victor , Muneeswaran Zilma P. , Raj Monika 
Published: November 2019

AbstractNitroalkanes react specifically with aldehydes, providing rapid, stable, and chemoselective protein bioconjugation. These nitroalkylated proteins mimic key post‐translational modifications (PTMs) of proteins and can be used to understand the role of these PTMs in cellular processes. Demonstrated here is the substrate scope of this bioconjugation by attaching a variety of tags, such as NMR tags, fluorescent tags, affinity tags, and alkyne tags, to proteins. The structure and enzymatic activity of modified proteins remain conserved after labeling. Notably, the nitroalkane group leads to easy characterization of proteins by mass spectrometry because of its distinct fingerprint pattern. Importantly, the nitro‐alkylated peptides provide a new handle for site‐selective fluorination of peptides, thus installing a specific probe to study peptide–protein interactions by19F NMR spectroscopy. Furthermore, nitroalkane reagents can be used for the late‐stage diversification of peptides and for the synthesis of peptide staples.
Adenosine Triphosphate‐Bioluminescence Technology as an Adjunct Tool to Validate Cleanliness of Surgical Instruments
Authors: Rodriguez Jose A. , Hooper Gwendolyn 
Published: November 2019

ABSTRACTPerioperative and sterile processing department personnel commonly use visual inspection to validate surgical instrument cleanliness. This validation process does not detect microbes (eg, bacteria, viruses) and the resultant inadequately decontaminated instruments can put patients at risk for developing surgical site infections. Sterile processing department personnel should use a rapid, straightforward method to validate surgical instrument cleanliness objectively. During a quality improvement project at a military treatment facility, staff members found that adenosine triphosphate (ATP)–based technology was a viable and affordable solution for detecting bioburden and validating cleaning practices. The project design compared manually and mechanically cleaned cannulated instruments (59 of each) and identified 16 contaminated instruments, 14 of which had been manually cleaned. The contamination rate after mechanical cleaning was significantly lower (P = .0022) compared with manual cleaning. As a result of this quality improvement project, this facility fully implemented the technology to validate instrument cleaning.
Investigation of Ni─Ca binary catalystic activities for production of light aromatics from catalytic pyrolysis of brown coal
Authors: Na Zhang , Xu Zhang , Ziliang Liu , Qiuxiang Lu , Wei Li , Qiue Cao , Xiaoguang Xie , Guini Yao , Zhigang Ma , Shenfu Yuan 
Published: November 2019

AbstractThe pyrolysis behavior of Ni─Ca‐loaded Yunnan brown coals (Shi Caoxing [SCX] and Guo Jiashan [GJS]) was studied in a fixed‐bed reactor to investigate the effects of Ni, Ca, and Ni─Ca loading on the yields of the obtained liquids and light aromatic hydrocarbons. Structural variations of the prepared coal chars were characterized by the scanning electron microscope–energy dispersion X‐ray, Fourier‐transform infrared spectroscopy, X‐ray diffractometer, Brunauer–Emmett–Teller analysis, and elemental analysis. The effects of the Ni, Ca, and Ni─Ca loadings on the tar yield and upgradation of pyrolysis tar were evaluated. The results revealed that the use of the Ni─Ca catalyst affords improved yields of the liquid products and tar. Furthermore, the light hydrocarbon liquids contents in the coal tar was improved with the use of the Ni─Ca catalyst. The heavy components and polycyclic aromatic hydrocarbons in the coal tar could be easy to convert into light hydrocarbon liquids (phenol, cresol, xylenols, and naphthalene) with the SCX brown coal pyrolysis. In contrast, the catalytic pyrolysis of GJS brown coal was inhibited by the Ni─Ca catalyst. The study revealed that the catalytic activity of the Ni─Ca catalyst greatly depends on the type of the coal substrate and was promoted or inhibited depending on the type of the brown coal.
Effect of compatibilizer concentration on dynamic rheological behavior and morphology of thermoplastic starch/polypropylene blends
Authors: Raee Ehsan , Avid Arezoo , Kaffashi Babak 
Published: November 2019

ABSTRACTThe reactive compatibilization of blends consisting polypropylene (PP) and thermoplastic starch (TPS) (70/30) with different portions of PP‐grafted maleic anhydride (PP‐g‐MA) is carried out by melt mixing. The esterification reaction between the starch hydroxyl and the PP‐g‐MA groups proved by the FTIR leads to a compatibility improvement. The dynamic rheological properties, morphology, elongation at break, and the impact strength of the blends were studied. The SEM images show that increasing the compatibilizer concentration reduces the dispersed TPS droplet size. The generalized Zener model states that an elastic interface is established (minimum α value) and enables us to predict the dynamic rheological properties of our blends in a longer frequency range to where the current experimental limitation exists. The modified Cross model is implemented to confirm better adhesion between phases when 20 wt % PP‐g‐MA is used (minimum ac value). The increase in the dynamic viscoelastic moduli at concentrations up to 20 wt % and the observed plateau at the elongation at break point at this concentration confirmed that this concentration is the optimum for the maximum stress transfer. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48742.
Are Sexually Offensive or Violent Experiences More Common among Adolescents Exposed to Parental Alcohol Intoxication?
Authors: Haugland Siri Havas , Coombes Lindsey , Strandheim Arve 
Published: November 2019

This study aimed to investigate the association between parental alcohol intoxication and sexually offensive or violent experiences in adolescence. A total of 8680 adolescents (13–16 years) participated in this cross‐sectional study. Analyses were based on adolescent self‐report on background, parental intoxication, and various sexually offensive and violent experiences. Multivariable logistic regression models were adjusted for gender, age and socioeconomic status. Seeing parents intoxicated a few times (lifetime) increased the odds of one or more violent experiences (odds ratio (OR) 2.1; 95% confidence interval (CI) 1.8–2.3) and one or more sexually offensive experiences (OR 2.3; CI 2.0–2.5). Seeing parents intoxicated a few times a year was strongly associated with one or more violent experiences (OR 2.7; CI 2.3–3.3) and one or more sexually offensive experiences (OR 2.8; CI 2.4–3.3). Finally, seeing parents intoxicated on some occasions weekly/monthly increased the odds for one or more violent experiences (OR 3.8; CI 2.9–4.8) and one or more sexually offensive experiences (OR 3.7; CI 2.9–4.7). The odds of adverse experience increased with the frequency of exposure to parental intoxication. However, even infrequent exposure to parental intoxication was clearly associated with these adverse childhood experiences. The findings identify a group that is potentially vulnerable to alcohol‐related harm. © 2019 John Wiley & Sons, Ltd.‘This study aimed to investigate the association between parental alcohol intoxication and sexually offensive or violent experiences in adolescence’Key Practitioner Messages

Sexually offensive or violent experiences among adolescents are consistently and strongly associated with parental intoxication.
Even a low frequency of exposure to parental intoxication is clearly associated with adverse childhood experiences.
The more frequently that adolescents are exposed to parental intoxication, the higher the odds of adverse experiences.
Findings identify a group that is potentially vulnerable to alcohol‐related harm and a possible target for preventive measures.
Halogen Bonding in Biomimetic Deiodination of Thyroid Hormones and their Metabolites and Dehalogenation of Halogenated Nucleosides
Authors: Mondal Santanu , Manna Debasish , Raja Karuppusamy , Mugesh Govindasamy 
Published: November 2019

AbstractThyroid hormones (THs) are key players in the endocrine system and play pivotal roles in carbohydrate and fat metabolism, protein synthesis, overall growth, and brain development. The thyroid gland predominantly produces thyroxine or 3,5,3′,5′‐tetraiodothyronine (T4) as a prohormone; three isoforms of a mammalian selenoenzyme—iodothyronine deiodinase (DIO1, DIO2 and DIO3)—catalyze the regioselective deiodination of T4 to produce biologically active and inactive metabolites. Whereas DIO1 catalyzes both 5‐ and 5′‐deiodination of T4, DIO2 and DIO3 selectively mediate 5‐ and 5′‐deiodination, respectively. In this review we discuss the regioselective deiodination of THs in the presence of organochalcogen compounds. Naphthalene‐based compounds containing sulfur and/or selenium at the peri positions mediate regioselective 5‐deiodination of THs, detailed mechanistic studies having revealed that the heterolytic cleavage of the C−I bond is facilitated by the formation of cooperative Se/S⋅⋅⋅I halogen bonds and Se/S⋅⋅⋅Se chalcogen bonds. We also discuss the biomimetic deiodination of several TH metabolites, including sulfated THs, iodothyronamines, and iodotyrosines. A brief discussion on the dehalogenation of halogenated nucleosides and nucleobases in the presence of organochalcogen compounds is also included.
Insights into the Control of Optoelectronic Properties in Mixed‐Stacking Charge‐Transfer Complexes
Authors: Wang Zongrui , Yu Fei , Xie Jian , Zhao Jianfeng , Zou Ye , Wang Zepeng , Zhang Qichun 
Published: November 2019

AbstractAlthough cocrystallization has provided a promising platform to develop new organic optoelectronic materials, it is still a big challenge to purposely design and achieve specific optoelectronic properties. Herein, a series of mixed‐stacking cocrystals (TMFA, TMCA, and TMTQ) were designed and synthesized, and the regulatory effects of the acceptors on the co‐assembly behavior, charge‐transfer nature, energy‐level structures, and optoelectronic characteristics were systematically investigated. The results demonstrate that it is feasible to achieve effective charge‐transport tuning and photoresponse switching by carefully regulating the intermolecular charge transfer and energy orbitals. The inherent mechanisms underlying the change in these optoelectronic behaviors were analyzed in depth and elucidated to provide clear guidelines for future development of new optoelectronic materials. In addition, due to the excellent photoresponsive characteristics of TMCA, TMCA‐based phototransistors were investigated with varying light wavelength and optical power, and TMCA shows the best performance among all reported cocrystals under UV illumination.