bluuebunny/crossref_metadata_2025_split huggingface dataset:
Individual‐Molecule Perspective Analysis of Chemical Reaction Networks: The Case of a Light‐Driven Supramolecular Pump
Authors: Sabatino Andrea , Penocchio Emanuele , Ragazzon Giulio , Credi Alberto , Frezzato Diego 
Published: August 2019

AbstractThe first study in which stochastic simulations of a two‐component molecular machine are performed in the mass‐action regime is presented. This system is an autonomous molecular pump consisting of a photoactive axle that creates a directed flow of rings through it by exploiting light energy away from equilibrium. The investigation demonstrates that the pump can operate in two regimes, both experimentally accessible, in which light‐driven steps can be rate‐determining or not. The number of photons exploited by an individual molecular pump, as well as the precision of cycling and the overall efficiency, critically rely on the operating regime of the machine. This approach provides useful information not only to guide the chemical design of a self‐assembling molecular device with desired features, but also to elucidate the effect of the environment on its performance, thus facilitating its experimental investigation.
Titanium‐Mediated Synthesis of Spirocyclic NH‐Azetidines from Oxime Ethers
Authors: Behnke Nicole Erin , Lovato Kaitlyn , Yousufuddin Muhammed , Kürti László 
Published: August 2019

AbstractThe TiIV‐mediated synthesis of spirocyclic NH‐azetidines from oxime ethers using either an alkyl Grignard reagent or terminal olefin ligand exchange coupling partner is described. Through a proposed Kulinkovich‐type mechanism, a titanacyclopropane intermediate forms and serves as a 1,2‐aliphatic dianion equivalent, inserting into the 1,2‐dielectrophilc oxime ether to ultimately give rise to the desired N‐heterocyclic four‐membered ring. This transformation proceeds in moderate yield to furnish previously unreported and structurally diverse NH‐azetidines in a single step.
Sorbents for the Direct Capture of CO2 from Ambient Air
Authors: Shi Xiaoyang , Xiao Hang , Azarabadi Habib , Song Juzheng , Wu Xiaolong , Chen Xi , Lackner Klaus S. 
Published: August 2019

AbstractThe urgency to address global climate change induced by greenhouse gas emissions is increasing. In particular, the rise in atmospheric CO2 levels is generating alarm. Technologies to remove CO2 from ambient air, or “direct air capture” (DAC), have recently demonstrated that they can contribute to “negative carbon emission.” Recent advances in surface chemistry and material synthesis have resulted in new generations of CO2 sorbents, which may drive the future of DAC and its large‐scale deployment. This Review describes major types of sorbents designed to capture CO2 from ambient air and they are categorized by the sorption mechanism: physisorption, chemisorption, and moisture‐swing sorption.
Development of Ubiquitin‐Based Probe for Metalloprotease Deubiquitinases
Authors: Hameed Dharjath S. , Sapmaz Aysegul , Burggraaff Lindsey , Amore Alessia , Slingerland Cornelis J. , van Westen Gerard J. P. , Ovaa Huib 
Published: August 2019

AbstractDeubiquitinases (DUBs) are a family of enzymes that regulate the ubiquitin signaling cascade by removing ubiquitin from specific proteins in response to distinct signals. DUBs that belong to the metalloprotease family (metalloDUBs) contain Zn2+ in their active sites and are an integral part of distinct cellular protein complexes. Little is known about these enzymes because of the lack of specific probes. Described here is a Ub‐based probe that contains a ubiquitin moiety modified at its C‐terminus with a Zn2+ chelating group based on 8‐mercaptoquinoline, and a modification at the N‐terminus with either a fluorescent tag or a pull‐down tag. The probe is validated using Rpn11, a metalloDUB found in the 26S proteasome complex. This probe binds to metalloDUBs and efficiently pulled down overexpressed metalloDUBs from a HeLa cell lysate. Such probes may be used to study the mechanism of metalloDUBs in detail and allow better understanding of their biochemical processes.
Construction of CoO/Co‐Cu‐S Hierarchical Tubular Heterostructures for Hybrid Supercapacitors
Authors: Lu Wen , Shen Junling , Zhang Peng , Zhong Yijun , Hu Yong , Lou Xiong Wen (David) 
Published: August 2019

AbstractHierarchical hollow structures for electrode materials of supercapacitors could enlarge the surface area, accelerate the transport of ions and electrons, and accommodate volume expansion during cycling. Besides, construction of heterostructures would enhance the internal electric fields to regulate the electronic structures. All these features of hierarchical hollow heterostructures are beneficial for promoting the electrochemical properties and stability of electrode materials for high‐performance supercapacitors. Herein, CoO/Co‐Cu‐S hierarchical tubular heterostructures (HTHSs) composed of nanoneedles are prepared by an efficient multi‐step approach. The optimized sample exhibits a high specific capacity of 320 mAh g−1 (2300 F g−1) at 2.0 A g−1 and outstanding cycling stability with 96.5 % of the initial capacity retained after 5000 cycles at 10 A g−1. Moreover, an all‐solid‐state hybrid supercapacitor (HSC) constructed with the CoO/Co‐Cu‐S and actived carbon shows a stable and high energy density of 90.7 Wh kg−1 at a power density of 800 W kg−1.
In situ compatibilization of a polyethylene, polypropylene, and polystyrene ternary blend through Friedel–Crafts alkylation
Authors: Carvalho Vinícius L. , Safieddine Camila , Demarquette Nicole R. , Pinheiro Luís A. 
Published: August 2019

ABSTRACTThe Friedel–Crafts alkylation reaction has been applied to reactively compatibilize a ternary blend of high‐density polyethylene (HDPE), polypropylene (PP), and polystyrene (PS). The reactions were carried out in an internal mixer using varying catalyst concentrations. The resulting compatibilizer was quantified after Soxhlet extraction. In addition, p‐substitution due to the grafting of alkyl groups onto the PS benzene ring was identified via nuclear magnetic resonance spectroscopy. The size of the PS domain in the reactive compositions is decreased by 80%. Moreover, the phase in which PS droplets were dispersed varied, that is, in the nonreactive blends they were found in the PP phase and in the reactive blends they shifted toward the HDPE phase. The effect of the compatibilizing agent was to improve the mechanical properties of the blend. Even with the lowest catalyst content, the properties of elongation‐at‐break, tensile strength, toughness, and elastic modulus showed improvements. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48295.
Influence of temperature during overmolding on the tensile modulus of self‐reinforced poly(ethylene terephthalate) insert
Authors: Jerpdal Lars , Schuette Philipp , Ståhlberg Daniel , åkermo Malin 
Published: August 2019

ABSTRACTSelf‐reinforced polymer composites are thermoplastic materials for design of recyclable lightweight components. The combination of sheet forming and subsequent overmolding from these materials allows an efficient manufacturing process with function integration. This article investigates how temperature exposure during an overmolding cycle influences the tensile modulus, shrinkage, and warpage for an insert made from self‐reinforced poly(ethylene terephthalate) (PET) when it is overmolded with polycarbonate (PC)/PET material. The temperature gradient that is induced by overmolding is simulated, and the results are validated through experiments. The results show that the insert reaches a temperature above the glass‐transition temperature for the matrix material in the main part of the insert, which leads to relaxation of residual stresses and thereby a reduction of the tensile modulus up to 18% for the insert after overmolding. Even though overmolding is an efficient process, it requires thorough knowledge of how temperature influences the material when applied to self‐reinforced composite materials. The study shows very interesting results, which can lead to new areas of applications for self‐reinforced PET. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020, 137, 48334.
Association of Inflammation With Pronociceptive Brain Connections in Rheumatoid Arthritis Patients With Concomitant Fibromyalgia
Authors: Kaplan Chelsea M. , Schrepf Andrew , Ichesco Eric , Larkin Tony , Harte Steven E. , Harris Richard E. , Murray Alison D. , Waiter Gordon D. , Clauw Daniel J. , Basu Neil 
Published: August 2019

ObjectiveRheumatoid arthritis (RA) patients with concomitant fibromyalgia (FM) exhibit alterations in brain connectivity synonymous with central sensitization. This study was undertaken to investigate how peripheral inflammation, the principal nociceptive stimulus in RA, interacts with brain connectivity in RA patients with FM.MethodsRA patients with concomitant FM and those without FM (FM+ and FM−, respectively; n = 27 per group) underwent functional connectivity magnetic resonance imaging. Seed‐to–whole‐brain functional connectivity analyses were conducted using seeds from the left mid/posterior insula and left inferior parietal lobule (IPL), which are regions that have been previously linked to FM symptoms and inflammation, respectively. The association between functional connectivity and erythrocyte sedimentation rate (ESR) was assessed in each group separately, followed by post hoc analyses to test for interaction effects. Cluster‐level, family‐wise error (FWE) rates were considered significant if the P value was less than 0.05.ResultsThe group of RA patients with FM and those without FM did not differ by age, sex, or ESR (P > 0.2). In FM+ RA patients, increased functional connectivity of the insula–left IPL, left IPL–dorsal anterior cingulate, and left IPL–medial prefrontal cortex regions correlated with higher levels of ESR (all FWE‐corrected P < 0.05). Post hoc interaction analyses largely confirmed the relationship between ESR and connectivity changes as FM scores increased.ConclusionWe report the first neurobiologic evidence that FM in RA may be linked to peripheral inflammation via pronociceptive patterns of brain connectivity. In patients with such “bottom‐up” pain centralization, concomitant symptoms may partially respond to antiinflammatory treatments.
A Nonaqueous Na‐Ion Hybrid Micro‐Supercapacitor with Wide Potential Window and Ultrahigh Areal Energy Density
Authors: Zhang Panpan , Wang Lanlan , Wang Faxing , Tan Deming , Wang Gang , Yang Sheng , Yu Minghao , Zhang Jian , Feng Xinliang 
Published: August 2019

AbstractThe increasing demand on smart miniaturized electronics has greatly boosted the development of high‐performance micro‐supercapacitors (MSCs). However, the unsatisfied electrochemical performance (e. g., narrow potential window, low areal energy density) impedes their wide applications. Here, we demonstrate a novel type of nonaqueous Na‐ion hybrid MSC, using VS2 nanosheets grown on electrochemically exfoliated graphene (VS2@EG) as the negative electrode and activated carbon as the positive electrode in nonaqueous sodium‐ion electrolyte. Such constructed nonaqueous Na‐ion hybrid MSCs show a remarkable areal capacitance of 110.7 mF cm−2 at 0.2 mA cm−2 in a wide potential range of 0.01–3.5 V and an outstanding areal energy density of 188.3 μWh cm−2. Besides, an impressive cycling stability up to 5000 cycles without noticeable decay is also achieved for the nonaqueous Na‐ion hybrid MSCs. This new hybrid MSC holds great potential application in on‐chip electronics.
Learning memory management with C‐Sim: A C‐based visual tool
Authors: Perez‐Schofield Baltasar García , Rivera Matías García , Ortin Francisco , Lado María J. 
Published: August 2019

AbstractNowadays, Computer Science (CS) students must cope with continuous challenges related to programming skill acquisition. In some occasions, they have to deal with the internals of memory management (pointers, pointer arithmetic, and heap management) facing a vision of programming from the low abstraction level offered by C. Even using C++ and references, not all scenarios where objects or collections of objects need to be managed can be covered. Based on the difficulties identified when dealing with such low‐level abstractions, the C‐Sim application, aimed at learning these concepts in an easy way, has been developed. To support the tool, the C programming language was selected. It allows showing concepts, remaining as close as possible both to the hardware and the operating system. To validate C‐Sim, pre and posttests were filled in by a group of 60 first‐year CS students, who employed the tool to learn about memory management. Grades of students using C‐Sim were also obtained and compared with those that did not use the tool the former academic year. As main outcomes, 82.26% of students indicated that they had improved programming and memory management knowledge, and 83.64% pointed out that the use of this type of tools improves the understanding and quality of the practice lessons. Furthermore, the marks of students have significantly increased. Finally, C‐Sim was designed from the ground up as a learning aid and can be useful for lecturers, who can complement their lessons using interactive demonstrations. Students can also employ it to experiment and learn autonomously.
Simulator‐based learning in the teaching of chemical engineering
Authors: Borreguero Ana M. , Valverde Jose L. , García‐Vargas Jesús M. , Sánchez‐Silva Luz 
Published: August 2019

AbstractAdvanced Chemical Processes subject used a learning methodology based on the practical cases solving and a global project work related with a process of the chemical industry. This subject has been raised at the University of Castilla–La Mancha (UCLM) as a nexus of knowledge, oriented towards the analysis of prospective flowsheets using simulators, such as Aspen Plus® and Aspen HYSYS®, applied to specific cases. This manuscript presents the activities, evaluating criteria, an example of the project work performed by students of the last year (sulfuric acid production) and the students’ satisfaction according to university surveys. The description of the project work example shows that the students were able to find and understand the data and information related to the industrial process suggested, using commercial software. Finally, the survey results for the subject evaluation conducted by the UCLM are shown, indicating high student satisfaction with the learning process.
Take Two – Implementing a Therapeutic Service for Children who have Experienced Abuse and Neglect: Beyond Evidence‐Informed Practice
Authors: Frederico Margarita , Jackson Annette , Black Carlina , Pawsey Ric , Cox Allison 
Published: August 2019

Helping children recover from the impact of child abuse and neglect is complicated by the limited evidence available on programme effectiveness and efficacy. This paper describes the implementation of a therapeutic service, in Victoria, Australia, known as Take Two, and provides a profile of client characteristics. The paper describes some of the barriers to children in the child protection system accessing therapeutic or mental health services and the approach attempted to overcome these barriers. The Take Two Practice Framework and the subsequent contribution of the Child Trauma Academy's Neurosequential Model of Therapeutics are discussed. There is exploration of evidence‐based practice and how this and related concepts are considered in the evolving theory of change and the Practice Framework. This includes consideration of what else is needed to supplement the evidence. The paper provides a useful model for other agencies that are planning or implementing a therapeutic programme for children traumatised by abuse and neglect.‘Describes the implementation of a therapeutic service, in Victoria, Australia, known as Take Two, and provides a profile of client characteristics’Key Practitioner Messages

Systematic reviews conclude that there is insufficient evidence to allow reliance on any single intervention with this client group.
This poses a genuine dilemma for services that aim to utilise evidence‐informed interventions but find their offerings limited.
Taking a research‐based and evidence‐informed approach with a strong theory of change has assisted one such programme to respond to this dilemma.
Cell Fuelling and Metabolic Energy Conservation in Synthetic Cells
Authors: Sikkema Hendrik R. , Gaastra Bauke F. , Pols Tjeerd , Poolman Bert 
Published: August 2019

AbstractWe are aiming for a blue print for synthesizing (moderately complex) subcellular systems from molecular components and ultimately for constructing life. However, without comprehensive instructions and design principles, we rely on simple reaction routes to operate the essential functions of life. The first forms of synthetic life will not make every building block for polymers de novo according to complex pathways, rather they will be fed with amino acids, fatty acids and nucleotides. Controlled energy supply is crucial for any synthetic cell, no matter how complex. Herein, we describe the simplest pathways for the efficient generation of ATP and electrochemical ion gradients. We have estimated the demand for ATP by polymer synthesis and maintenance processes in small cell‐like systems, and we describe circuits to control the need for ATP. We also present fluorescence‐based sensors for pH, ionic strength, excluded volume, ATP/ADP, and viscosity, which allow the major physicochemical conditions inside cells to be monitored and tuned.
Safety and efficacy of hybrid vascular closure technique using both a suture‐ and collagen‐mediated closure device after transfemoral transcatheter aortic valve implantation
Authors: Al‐Ani Ahmed , Hoffmann Pavel , von Lueder Thomas , Opdahl Anders 
Published: August 2019

AbstractObjectivesTo evaluate the clinical utility and feasibility of a hybrid technique for obtaining vascular hemostasis by combining a suture‐ and a collagen‐mediated system after transfemoral transcatheter aortic valve implantation (TF TAVI) in a real‐world setting.MethodsIn 75 consecutive TF TAVI procedures, we investigated a hybrid closing method to achieve hemostasis at the large bore puncture site using a combination of one presuture closure system (ProGlide) and one collagen‐mediated system (Angio‐Seal). Vascular complications at puncture site were recorded until discharge.ResultsSuccessful hemostasis by the hybrid technique was achieved in 74 out of 75 patients, and the method was well tolerated by all patients. In 73 patients, (97.3%) neither puncture site related complications nor serious early or late bleedings were observed during a median hospital stay of 2 days postprocedure.ConclusionThis single‐center registry study indicates that a percutaneous hybrid closure technique is safe and efficacious in closing large bore arteriotomies. It is an easy and reliable technique that may contribute to simplifying TAVI procedures.Study registrationThe data was collected from an internal quality control registry on treatment of patients with valvular heart disease with or without coronary artery disease, No 2014/17280, Oslo University Hospital, Ullevål.
Aortic dissection after transcatheter aortic valve replacement
Authors: Martinez Quintero Beatriz , Voss Matthew R. 
Published: August 2019

AbstractAortic dissection is a rare but life‐ threatening complication of transcatheter aortic valve replacement, clinicians should be aware of this complication and should consider timely diagnostic evaluations, as well as, establish a prompt treatment plan based on a multidisciplinary team approach.
Confined Metal Sulfides Nanoparticles into Porous Carbon Nanosheets with Surface‐Controlled Reactions for Fast and Stable Lithium‐Ion Batteries
Authors: Sun Dongfei , Wang Li , Li Yanli , Yang Yaoxia , Zhou Xiaozhong , Ma Guofu , Lei Ziqiang 
Published: August 2019

AbstractTo achieve high‐performance lithium‐ion batteries (LIBs), the ion diffusion behavior in electrode materials is a challenging issue. Herein, 2D FeS/porous carbon nanosheets (FeS@PCSs) hybrids were successfully prepared by a facile, low‐cost strategy involving metal salt‐assisted chemical vapor deposition (CVD) and in situsulfuration process. The unique 2D structure is conducive to shorten the ion diffusion distance, buffer the volume change of FeS nanoparticles, as well as provide abundant sites for Li+ storage. Benefiting from the unique structure, the FeS@PCSs electrode exhibits high surface reaction contributions. When investigated as an anode for lithium‐ion batteries, the as‐prepared FeS@PCSs electrode exhibits a high reversible capacity (1026.2 mAh g−1 at 0.1 A g−1), excellent rate capability (647.2 mAh g−1 at 5 A g−1 and 561.1 mAh g−1 at 10 A g−1), and outstanding cycling stability (888.7 mAh g−1 at 1.0 A g−1 over 800 cycles). This work provides a cost‐effective and scalable route to synthesis the 2D carbon‐based transition metal compounds as high‐performance LIBs anodes.
PAH/PAH(CF3)n Donor/Acceptor Charge‐Transfer Complexes in Solution and in Solid‐State Co‐Crystals
Authors: Castro Karlee P. , Bukovsky Eric V. , Kuvychko Igor V. , DeWeerd Nicholas J. , Chen Yu‐Sheng , Deng Shihu H. M. , Wang Xue‐Bin , Popov Alexey A. , Strauss Steven H. , Boltalina Olga V. 
Published: August 2019

AbstractA solution, solid‐state, and computational study is reported of polycyclic aromatic hydrocarbon PAH/PAH(CF3)n donor/acceptor (D/A) charge‐transfer complexes that involve six PAH(CF3)n acceptors with known gas‐phase electron affinities that range from 2.11(2) to 2.805(15) eV and four PAH donors, including seven CT co‐crystal X‐ray structures that exhibit hexagonal arrays of mixed π‐stacks with 1/1, 1/2, or 2/1 D/A stoichiometries (PAH=anthracene, azulene, coronene, perylene, pyrene, triphenylene; n=5, 6). These are the first D/A CT complexes with PAH(CF3)n acceptors to be studied in detail. The nine D/A combinations were chosen to allow several structural and electronic comparisons to be made, providing new insights about controlling D/A interactions and the structures of CT co‐crystals. The comparisons include, among others, CT complexes of the same PAH(CF3)n acceptor with four PAH donors and CT complexes of the same donor with four PAH(CF3)n acceptors. All nine CT complexes exhibit charge‐transfer bands in solution with λmax between 467 and 600 nm. A plot of E(λmax) versus [IE(donor)−EA(acceptor)] for the nine CT complexes studied is linear with a slope of 0.72±0.03 eV eV−1. This plot is the first of its kind for CT complexes with structurally related donors and acceptors for which precise experimental gas‐phase IEs and EAs are known. It demonstrates that conclusions based on the common assumption that the slope of a CT E(λmax) versus [IE−EA] plot is unity may be incorrect in at least some cases and should be reconsidered.
Photoinitiated Charge Transfer in a Triangular Silver(I) Hydride Complex and Its Oxophilicity
Authors: Kruppa Sebastian V. , Groß Cedric , Gui Xin , Bäppler Florian , Kwasigroch Björn , Sun Yu , Diller Rolf , Klopper Wim , Niedner‐Schatteburg Gereon , Riehn Christoph , Thiel Werner R. 
Published: August 2019

AbstractInvited for the cover of this issue are the research groups of Rolf Diller, Gereon Niedner‐Schatteburg, Christoph Riehn and Werner R. Thiel from the TU Kaiserslautern (TUK) and the group of Wim Klopper of the Karlsruhe Institute of Technology (KIT) collaborating within the research center “3MET” (SFB/TRR 88). The image depicts the photoinitiated charge transfer within a phosphine‐stabilized triangular silver hydride complex. Read the full text of the article at 10.1002/chem.201901981.