bluuebunny/crossref_metadata_2025 huggingface dataset:
Recent Progress in 2D Metal‐Organic Frameworks for Optical Applications
Authors: Zheng Yongshen , Sun Fang‐Zhou , Han Xiao , Xu Jialiang , Bu Xian‐He
Published: May 2020

2D metal‐organic frameworks (MOFs) have attracted broad research interest in recent years owing to their unique dimension‐related properties for widespread applications in catalysis, energy storage, conductivity, and optoelectronic devices. In this review, first the strategies for the rational design and precise construction of 2D MOFs are introduced. Then, the synthesis of 2D MOFs and their nanosheets by using top‐down and bottom‐up methods are summarized. Subsequently, the recent advances in optical/photonic applications of these 2D MOFs are highlighted, with special focus on lighting and display devices, nonlinear optics, as well as the luminescent sensing and biomedicine applications. Finally, the future potentials and challenges for the construction of 2D MOFs for optical materials are outlooked.
Blue Perovskite Nanocrystal Light‐Emitting Devices via the Ligand Exchange with Adamantane Diamine
Authors: Chiba Takayuki , Ishikawa Shota , Sato Jun , Takahashi Yoshihito , Ebe Hinako , Ohisa Satoru , Kido Junji
Published: May 2020

Metal halide perovskite nanocrystals (NCs) have been established as promising materials for light‐emitting devices (LEDs) due to their interesting optoelectrical properties, including high photoluminescence quantum yield (PLQY) and high color purity with narrow full width at half maximum (FWHM). However, blue perovskite LEDs, with an emission wavelength below 470 nm, require further investigation to improve their performance. Here, it is demonstrated that mixed‐halide CsPb(Cl/Br)3 NCs prepared by ligand exchange with the rigid bidentate structure of adamantane‐1,3‐diamine (ADDA) can be used for blue LEDs. The ligand exchange of CsPb(Cl/Br)3 NCs with ADDA improves PLQY without changing the peak wavelength and FWHM. The LEDs based on ligand exchange NCs with ADDA show an external quantum efficiency (EQE) of 0.49%. Moreover, a quaternary ammonium salt, oleylammonium chloride (OAM‐Cl), is also investigated as an interfacial layer to reduce current density. The LED fabricated with OAM‐Cl reaches an EQE of 1.1% and luminance of 43.2 cd m−2 at the electroluminescence wavelength of 456 nm, representing significantly higher performance compared to that of LEDs without OAM‐Cl layers. Therefore, the ligand exchange of NCs with ADDA and the use of a passivation layer comprising OAM‐Cl facilitate an improvement in the LED performance.
Structural Control of the Molecular Packing and Dynamics of Mechanofluorochromic Materials Based on Small Donor–Acceptor Systems with Turn‐On Luminescence
Authors: Josse Pierre , Allain Magali , Calupitan Jan Patrick , Jiang Yue , Cabanetos Clément , Roncali Jean
Published: May 2020

A series of simple donor–acceptor molecules consisting of an oligo‐oxyethylene (OOE) N‐substituted diphenylamine connected to a dicyanovinyl (DCV) acceptor group by a thienyl π‐conjugating spacer are synthesized. Amorphous deep‐red freshly cast thin films rapidly evolve towards an almost colorless pale beige poly‐crystalline stable material from which a deep‐red photoluminescent state can be switched‐on by mechanical stimulation. The effects of the length of the OOE chain on the molecular packing of the material and on the dynamics of the recovery process and aggregation in solution are analyzed. Crystallographic results show that the length of the OOE chain directly controls the molecular packing from head‐to‐tail arrangement of the dipoles for short chain to co‐facial dimers leading to a non‐centrosymmetric material with nonlinear optics (NLO) activity for the longer ones. The analysis of the dynamics of the self‐recovery process of thin films and of molecular aggregation in solution shows that the dynamics of both processes is directly controlled by the length of the OOE chain. Since, as confirmed by optical and electrochemical results, the OOE substituents have strictly no influence on the electronic properties of the π‐conjugated system, the observed effects are unambiguously related to changes in intermolecular interactions.
Side by Side Battery Technologies with Lithium‐Ion Based Batteries
Authors: Durmus Yasin Emre , Zhang Huang , Baakes Florian , Desmaizieres Gauthier , Hayun Hagay , Yang Liangtao , Kolek Martin , Küpers Verena , Janek Jürgen , Mandler Daniel , Passerini Stefano , Ein‐Eli Yair
Published: May 2020

In recent years, the electrochemical power sources community has launched massive research programs, conferences, and workshops on the “post Li battery era.” However, in this report it is shown that the quest for post Li‐ion and Li battery technologies is incorrect in its essence. This is the outcome of a three day discussion on the future technologies that could provide an answer to a question that many ask these days: Which are the technologies that can be regarded as alternative to Li‐ion batteries? The answer to this question is a rather surprising one: Li‐ion battery technology will be here for many years to come, and therefore the use of “post Li‐ion” battery technologies would be misleading. However, there are applications with needs for which Li‐ion batteries will not be able to provide complete technological solutions, as well as lower cost and sustainability. In these specific cases, other battery technologies will play a key role. Here, the term “side‐by‐side technologies” is coined alongside a discussion of its meaning. The progress report does not cover the topic of Li‐metal battery technologies, but covers the technologies of sodium‐ion, multivalent, metal–air, and flow batteries.
Recent Advances in Perovskite‐Type Oxides for Energy Conversion and Storage Applications
Authors: Sun Chunwen , Alonso Jose A. , Bian Juanjuan
Published: May 2020

Professor John B. Goodenough started his research on perovskite‐type oxides working on random‐access memory with ceramic [La,M(II)]MnO3 in the Lincoln Laboratory, Massachusetts Institute of Technology, more than 60 years ago. Since then perovskite‐type oxides have played vital roles in the field of energy conversion and storage. In this review, a brief overview is given on the structure, defect chemistry, and transport properties of perovskite oxides, especially the mixed‐valent materials with mixed electronic and ionic conductivities. The recent advances of perovskite oxides applications in the oxygen reduction reaction, oxygen evolution reaction, electrochemical water splitting reaction, metal–air batteries, solid‐state batteries, oxygen separation membranes, and solid oxide fuel cells are highlighted. Moreover, some novel design strategies for optimizing performance, like interface engineering, defect engineering, strain modulation are discussed as well. Finally, a perspective is given on how to design high‐performance perovskite oxide based materials for energy conversion and storage applications as well as the challenges involved in this task.
Smell and taste symptom‐based predictive model for COVID‐19 diagnosis
Authors: Roland Lauren T. , Gurrola Jose G. , Loftus Patricia A. , Cheung Steven W. , Chang Jolie L.
Published: May 2020

Background

The presentation of coronavirus 2019 (COVID‐19) overlaps with common influenza symptoms. There is limited data on whether a specific symptom or collection of symptoms may be useful to predict test positivity.

Methods

An anonymous electronic survey was publicized through social media to query participants with COVID‐19 testing. Respondents were questioned regarding 10 presenting symptoms, demographic information, comorbidities, and COVID‐19 test results. Stepwise logistic regression was used to identify predictors for COVID‐19 positivity. Selected classifiers were assessed for prediction performance using receiver operating characteristic (ROC) curve analysis.

Results

A total of 145 participants with positive COVID‐19 testing and 157 with negative results were included. Participants had a mean age of 39 years, and 214 (72%) were female. Smell or taste change, fever, and body ache were associated with COVID‐19 positivity, and shortness of breath and sore throat were associated with a negative test result (p < 0.05). A model using all 5 diagnostic symptoms had the highest accuracy with a predictive ability of 82% in discriminating between COVID‐19 results. To maximize sensitivity and maintain fair diagnostic accuracy, a combination of 2 symptoms, change in sense of smell or taste and fever was found to have a sensitivity of 70% and overall discrimination accuracy of 75%.

Conclusion

Smell or taste change is a strong predictor for a COVID‐19–positive test result. Using the presence of smell or taste change with fever, this parsimonious classifier correctly predicts 75% of COVID‐19 test results. A larger cohort of respondents will be necessary to refine classifier performance.
Planar Spoof Surface Plasmon Polariton Antenna by Using Transmissive Phase Gradient Metasurface
Authors: Wang Dengpan , Wang Guangming , Cai Tong , Liu Kaiyue , Li Haipeng , Mao Ruiqi , Wu Borui
Published: May 2020

Spoof surface plasmon polariton (SSPP) antennas are of particular importance in communication and radar systems. Currently available SSPP radiation devices are limited to low performance with high side‐lobes because it is extremely challenging to accurately control the wave vector of SSPP and the inherent momentum mismatch between the SSPP and spatial waves. Inspired by the optical principle of reversibility, high‐performance radiation control of SSPP is proposed to be achieved with transmissive phase gradient metasurface (TPGM). The TPGM, placed a meticulously optimized distance above the SSPP propagation structure, can provide an additional opposite wave vector to match the momentum between the SSPP and spatial waves. When the propagating SSPP transmits on the TPGM, it can be decoupled into the free space accurately and flexibly. Numerical results coincide well with the measurements, indicating that the radiation control of SSPP achieves high‐performance and low side‐lobe within 9 to 10.5 GHz with the measured radiation efficiency higher than 50%. The measured maximum efficiency appears at 9.8 GHz for 69%. Thanks to the flexible and accurate manipulation of the dispersion relation of SSPP provided by TPGM, the findings may open an avenue in achieving larger angle scanning antenna.
Base‐Assisted Imidization: A Synthetic Method for the Introduction of Bulky Imide Substituents to Control Packing and Optical Properties of Naphthalene and Perylene Imides
Authors: Mahl Magnus , Shoyama Kazutaka , Krause Ana‐Maria , Schmidt David , Würthner Frank
Published: May 2020

We report the direct imidization of naphthalene and perylene dicarboxylic anhydrides/esters with bulky ortho,ortho‐diaryl‐ and ortho,ortho‐dialkynylaniline derivatives. This imidization method uses n‐butyllithium as a strong base to increase the reactivity of bulky amine derivatives, proceeds under mild reaction conditions, requires only stoichiometric amounts of reactants and gives straightforward access to new sterically crowded rylene dicarboximides. Mechanistic investigations suggest an isoimide as intermediary product, which was converted to the corresponding imide upon addition of an aqueous base. Single‐crystal X‐ray diffraction analyses reveal dimeric packing motifs for monoimides, while two‐side shielded bisimides crystallize in isolated molecules without close π–π‐interactions. Spectroscopic investigations disclose the influence of the bulky substituents on the optical properties in the solid state.
Hyaluronic‐Acid‐Presenting Self‐Assembled Nanoparticles Transform a Hyaluronidase HYAL1 Substrate into an Efficient and Selective Inhibitor
Authors: Duan Haohao , Donovan Mark , Hernandez Franck , Di Primo Carmelo , Garanger Elisabeth , Schultze Xavier , Lecommandoux Sébastien
Published: May 2020

In this study, an original method of macromolecular design was used to develop a hyaluronidase‐1 (HYAL1) inhibitor from its principal substrate, hyaluronic acid (HA). HA‐based nanoparticles (HA‐NP) were obtained by copolymer self‐assembly and their effects on HYAL1 activity were investigated by combining different analytical tools. Compared to HA, HA‐NP exhibited an enhanced stability against HYAL1 degradation while maintaining its interaction with the HA receptors CD44 and aggrecan. HA‐NP displayed a strong and selective inhibition of HYAL1 activity and retarded the hydrolysis of higher‐molar‐mass HA in solution. A co‐nanoprecipitation process was used to formulate a range of hybrid nanoparticle samples, which demonstrated the specificity and efficiency of HA‐NP in HYAL1 inhibition.
Fast near infrared light response hydrogel as medical dressing for wound healing
Authors: Yang Kai , Yin Xinyu , Yan Yuanyang , Luo Guanzhou , Xu Mengyi , Pi Pihui , Xu Shouping , Wen Xiufang
Published: May 2020

Fast‐response smart hydrogels with combination of appropriate mechanical strength, self‐healing and tissue adhesiveness ability, and controllable drug release performance are highly desired as wound dressing practice. Herein, a novel dual‐crosslinking hydrogel with gold nanorods (AuNRs) well dispersed in its polymer network, D‐hydrogel@AuNR, was constructed via ultraviolet light initiated radical copolymerization of acrylamide (AM), isopropylacrylamide (NIPAAM), and dopamine methacrylamide (DMA) in a complex solution of AuNRs and cysteamine‐grafted oxidized sodium alginate (OSA‐SH). The produced D‐hydrogel@AuNR exhibits fast response to the near infrared light (NIR, 808 nm) exposure and a cumulative release level of encapsulated gentamicin sulfate (GS) up to 75% within 60 s laser irradiation. The dual‐crosslinking network that the first MBA crosslinked P(AM‐co‐NIPAAM‐co‐DMA) network and the second imine bonded network makes the tensile stress and tensile strain of D‐hydrogel@AuNR could reach up to 397.0 k Pa and 240%, respectively. Moreover, the received D‐hydrogel@AuNR also exhibits remarkable self‐healing ability and excellent cell affinity and tissue adhesiveness. These desirable properties of D‐hydrogel@AuNR together make it an appropriate candidate for practical wound dressing under different biomedical conditions.
Risiko der Wasserstoffentwicklung an martensitischen Schraubankern unter baupraktischen Bedingungen
Authors: Müller Thoralf , Ebell Gino , Burkert Andreas
Published: May 2020

Die vorliegende Untersuchung beschäftigt sich mit der Fragestellung, ob unter praxisrelevanten Bedingungen die Entstehung von Wasserstoff an vollmartensitischen Schraubankern möglich ist. Im Gegensatz zu austenitischen Werkstoffen besteht bei martensitischen Werkstoffen bei Gegenwart von Wasserstoff stets die Möglichkeit einer wasserstoffinduzierten Versprödung des Materials. Hierfür wurde ein in der Praxis häufig anzutreffendes Szenario gewählt, das ein galvanisches Element, bestehend aus nichtrostenden Schraubankern (in diesem Fall martensitischen) und einer verzinkten Ankerplatte an einem Betonkörper, umfasst. Zum Nachweis einer Wasserstoffentwicklung werden der Elementstrom zwischen den Bauteilen sowie das Korrosionspotential erfasst. Die Ergebnisse der Versuche zeigen, dass über eine zeitlich begrenzte Dauer eine starke kathodische Polarisation der martensitischen Schraubanker durch die korrosive Auflösung des Zinks erfolgt. Als Folge kommt es zur Wasserzersetzung im Phasengrenzbereich der Schraubanker und zur Entstehung von atomarem Wasserstoff. Das berechnete Gasvolumen des entstandenen Wasserstoffs an den Stahlankern wurde bestimmt und lag im Mittel bei 11,14 ± 1,94 ml. Eine Diffusion des an der Stahloberfläche adsorbierten Wasserstoffs in den martensitischen Werkstoff ist somit theoretisch möglich und impliziert eine mögliche Gefährdung durch wasserstoffinduzierte Rissbildung und spontanes Versagen unter Belastung.
Effect of redox‐responsive DTSSP crosslinking on poly(l‐lysine)‐grafted‐poly(ethylene glycol) nanoparticles for delivery of proteins
Authors: Seaberg Joshua , Flynn Nicholas , Cai Amanda , Ramsey Joshua D.
Published: May 2020

Therapeutic proteins are utilized in a variety of clinical applications, but side effects and rapid in vivo clearance still present hurdles. An approach that addresses both drawbacks is protein encapsulation within in a polymeric nanoparticle, which is effective but introduces the additional challenge of destabilizing the nanoparticle shell in clinically relevant locations. This study examined the effects of crosslinking self‐assembled poly(l‐lysine)‐grafted‐poly(ethylene glycol) nanoparticles with redox‐responsive 3,3′‐dithiobis(sulfosuccinimidyl propionate) (DTSSP) to achieve nanoparticle destabilization in a reductive environment. The polymer‐protein nanoparticles (DTSSP NPs) were formed through electrostatic self‐assembly and crosslinked with DTSSP, which contains a glutathione‐reducible disulfide. As glutathione is upregulated in various cancers, DTSSP NPs could display destabilization within cancer cells. A library of DTSSP NPs was formed with varying copolymer to protein (C:P) and crosslinker to protein (X:P) mass ratios and characterized by size and encapsulation efficiency. DTSSP NPs with a 7:1 C:P ratio and 2:1 X:P ratio were further characterized by stability in the presence proteases and reducing agents. DTSSP NPs fully encapsulated the model protein and displayed 81% protein release when incubated with 5 mM dithiothreitol for 12 hr. This study contributes to understanding stimulus‐responsive crosslinking of polymeric nanoparticles and could be foundational to clinical administration of therapeutic proteins.
Patient and clinician experience of a serious illness conversation guide in oncology: A descriptive analysis
Authors: Paladino Joanna , Koritsanszky Luca , Nisotel Lauren , Neville Bridget A. , Miller Kate , Sanders Justin , Benjamin Evan , Fromme Erik , Block Susan , Bernacki Rachelle
Published: May 2020

Background/objective

Oncology guidelines recommend earlier communication with patients about prognosis and goals‐of‐care in serious illness. However, current evidence leaves gaps in our understanding of the experience of these conversations. This analysis evaluates the patient and clinician experience of a conversation using a Serious Illness Conversation Guide (SICG).

Design/setting

Secondary analysis from a cluster‐randomized clinical trial in a northeastern cancer center.

Participants

Physicians, advanced practice clinicians, and patients with advanced cancer who received the intervention.

Intervention

SICG, clinician training, systems‐changes.

Main outcomes and measures

The patient questionnaire assessed perceptions of the conversation and impact on anxiety, hopefulness, peacefulness, sense of control over medical decisions, closeness with their clinician, and behaviors. The clinician questionnaire assessed feasibility, acceptability, and impact on satisfaction in their role.

Results

We enrolled 54 clinicians and 163 patients; 41 clinicians and 118 patients had a SICG discussion. Most patients described the conversation as worthwhile (79%) and reported no change or improvement in their sense of peacefulness, hopefulness, and anxiety (on average 79%); 56% reported feeling closer with their clinician. Qualitative patient data described positive behavior changes, including enhanced planning for future care and increased focus on personal priorities. Nearly 90% of clinicians agreed that the SICG facilitated timely, effective conversations, and 70% reported increased satisfaction in their role.

Conclusion

Conversations using a SICG were feasible, acceptable, and were associated with positive experiences for both patients and clinicians in oncology in ways that align with national recommendations for serious illness communication. This trial is registered at ClinicalTrials.gov: NCT01786811 https://clinicaltrials.gov/ct2/show/NCT01786811.
New Multicomponent MoVSbNbCeOx/SiO2 Catalyst with Enhanced Catalytic Activity for Oxidative Dehydrogenation of Ethane to Ethylene
Authors: Zenkovets Galina A. , Shutilov Alexey A. , Bondareva Valentina M. , Sobolev Vladimir I. , Marchuk Alexander S. , Tsybulya Sergey V. , Prosvirin Igor P. , Ishchenko Arcady V. , Gavrilov Vladimir Yu.
Published: May 2020

In our study, we have obtained a multicomponent MoVSbNbCeOx/SiO2 catalyst with high catalytic activity for oxidative dehydrogenation of ethane (ODE) to ethylene. To date, multicomponent MoVTe(Sb)NbOx catalysts, which have been intensively studied during the last years, were found as very promising for the ODE to produce ethylene. It was generally agreed that the MoVTeNbOx catalyst was more efficient than MoVSbNbOx. The major drawback of using Te‐containing catalysts is the presence of environmentally harmful, toxic tellurium, and its volatility during the catalyst preparation and catalytic reaction conditions. In our work, the Mo1V0.24Sb0.23Nb0.08Ce0.01Ox/50 wt. % SiO2 catalyst was prepared via the spray‐dry method of aqueous solutions of the starting components, followed by heat‐treatment in He at 350 and 600 °C. For comparative purpose, one of the best Te‐containing catalysts Mo1V0.3Te0.23Nb0.12Ox was also tested in this reaction under the similar reaction conditions. A comparison of the catalytic properties of Sb− and Te− containing catalysts at the reaction temperature of 400–450 °C illustrates for both catalysts relatively high catalytic properties for ODE. The yield of ethylene of ca. 74 % was obtained for these catalysts, which exceeds the best yield reported in literature for Sb‐containing catalysts. The two main phases – M1 and M2 were revealed by XRD in the Sb‐containing catalyst. Intergrowth between the crystals of M1 and M2 phases with the formation of the interphase boundary in the highly active and selective Sb‐containing catalyst can be proposed from HRTEM results. The nature of the active state in this catalyst is discussed.
A Supramolecular Model for the Co‐Catalytic Role of Nitro Compounds in Brønsted Acid Catalyzed Reactions
Authors: Montalvo‐Acosta Joel J. , Dryzhakov Marian , Richmond Edward , Cecchini Marco , Moran Joseph
Published: May 2020

Nitro compounds are known to change reaction rates and kinetic concentration dependence of Brønsted‐acid‐catalyzed reactions. Yet, no mechanistic model exists to account for these observations. In this work, an atomistic model for the catalytically active form for an alcohol dehydroazidation reaction is presented, which is generated by DFT calculations and consists of an H‐bonded aggregate of two molecules of Brønsted acid and two molecules of nitro compound. The computed O−H stretching frequencies for the aggregate indicate they are stronger acids than the individual acid molecules and serve as predictors for experimental reaction rates. By applying the model to a chemically diverse set of potential promoters, it was predicted and verified experimentally that sulfate esters induce a similar co‐catalytic effect. The important implication is that Brønsted‐acid catalysis must be viewed from a supramolecular perspective that accounts for not only the pKa of the acid and the bulk properties of a solvent, but also the weak interactions between all molecules in solution.
Modulation of the Self‐Assembly of π‐Amphiphiles in Water from Enthalpy‐ to Entropy‐Driven by Enwrapping Substituents
Authors: Syamala Pradeep P. N. , Würthner Frank
Published: May 2020

Depending on the connectivity of solubilizing oligoethylene glycol (OEG) side chains to the π‐cores of amphiphilic naphthalene and perylene bisimide dyes, self‐assembly in water occurs either upon heating or cooling. Herein, we show that this effect originates from differences in the enwrapping capability of the π‐cores by the OEG chains. Rylene bisimides bearing phenyl substituents with three OEG chains attached directly to the hydrophobic π‐cores are strongly sequestered by the OEG chains. These molecules self‐assemble at elevated temperatures in an entropy‐driven process according to temperature‐ and concentration‐dependent UV/Vis spectroscopy and calorimetric dilution studies. In contrast, for rylene bisimides in which phenyl substituents with three OEG chains are attached via a methylene spacer, leading to much weaker sequestration, self‐assembly originates upon cooling in an enthalpy‐driven process. Our explanation for this controversial behavior is that the aggregation in the latter case is dictated by the release of “high energy water” from the hydrophobic π‐surfaces as well as dispersion interactions between the π‐scaffolds which drive the self‐assembly in an enthalpically driven process. In contrast, for the former case we suggest that in addition to the conventional explanation of a dehydration of hydrogen‐bonded water molecules from OEG units it is in particular the increase in conformational entropy of back‐folded OEG side chains upon aggregation that provides the pronounced gain in entropy that drives the aggregation process. Thus, our studies revealed that a subtle change in the attachment of solubilizing substituents can switch the thermodynamic signature for the self‐assembly of amphiphilic dyes in water from enthalpy‐ to entropy‐driven.
Short Total Synthesis of Ajoene, (E,Z)‐4,5,9‐Trithiadodeca‐1,6,11‐triene 9‐oxide, in Batch and (E,Z)‐4,5,9‐Trithiadodeca‐1,7,11‐triene in Continuous Flow
Authors: Raynbird Marina Yamamoto , Silva Filipa , Smallman Harry , Khokhar Shaista S. , Neef Daniel , Evans Gareth J. S. , Wirth Thomas
Published: May 2020

A short total synthesis of ajoene, (E,Z)‐4,5,9‐trithiadodeca‐1,6,11‐triene 9‐oxide, has been achieved over six steps. In addition, a continuous flow synthesis under mild reaction conditions to (E,Z)‐4,5,9‐trithiadodeca‐1,7,11‐triene is described starting from simple and easily accessible starting materials. Over four steps including propargylation, radical addition of thioacetate, deprotection, and disulfide formation/ allylation, the target product can be obtained at a rate of 0.26 g h−1 in an overall yield of 12 %.
Thiophene and Selenophene Binding at a Pd3 Cluster Site
Authors: Yamamoto Koji , Sawada Junya , Murahashi Tetsuro
Published: May 2020

We report the triply bridging coordination of thiophene and selenophene to a trinuclear metal cluster site. The triply bridging coordination of selenophene at a Pd3 site forms a unique spiro‐type Pd5 cluster. Furthermore, either thiophene or selenophene is accommodated stably at a Pd3 site supported by a backside μ3‐cyclooctatetraene ligand through the face‐capping μ3‐coordination. The Pd3 site supported by the cyclooctatetraene ligand showed higher binding affinity of benzene over thiophene, although a Pd2 site strongly favors thiophene over benzene.
Calculating the Reaction Order and Activation Energy for the Hydrothermal Carbonization of Fructose
Authors: Jung Dennis , Körner Paul , Kruse Andrea
Published: May 2020

The development of accurate kinetic models for hydrothermal carbonization (HTC) faces major difficulties. This is related to the fact that the formation of the solid hydrochar can be regarded as a formation of a second phase from a homogenous solution. The reaction mechanism is not fully understood. From the current state of art, it is obvious that the reaction mechanism is some sort of polymerization reaction, thus, having reaction order higher than one. In order to gain more knowledge about the HTC reaction, fructose is used as a model substance, as it can be regarded as a key intermediate during the hydrothermal processing of carbohydrates. The results indicate that the reaction order is a highly sensitive parameter varying with temperature, reaction time and initial concentration. It can be concluded that the model itself is a strong simplification of the real reaction mechanism, thus more research is necessary to complete the actual knowledge.
Spectrum of driver mutations and clinical impact of circulating tumor DNA analysis in non–small cell lung cancer: Analysis of over 8000 cases
Authors: Mack Philip C. , Banks Kimberly C. , Espenschied Carin R. , Burich Rebekah A. , Zill Oliver A. , Lee Christine E. , Riess Jonathan W. , Mortimer Stefanie A. , Talasaz AmirAli , Lanman Richard B. , Gandara David R.
Published: May 2020

Background

Circulating cell‐free tumor DNA (ctDNA)‐based mutation profiling, if sufficiently sensitive and comprehensive, can efficiently identify genomic targets in advanced lung adenocarcinoma. Therefore, the authors investigated the accuracy and clinical utility of a commercially available digital next‐generation sequencing platform in a large series of patients with non–small cell lung cancer (NSCLC).

Methods

Plasma‐based comprehensive genomic profiling results from 8388 consecutively tested patients with advanced NSCLC were analyzed. Driver and resistance mutations were examined with regard to their distribution, frequency, co‐occurrence, and mutual exclusivity.

Results

Somatic alterations were detected in 86% of samples. The median variant allele fraction was 0.43% (range, 0.03%‐97.62%). Activating alterations in actionable oncogenes were identified in 48% of patients, includingEGFR(26.4%),MET(6.1%), andBRAF(2.8%) alterations and fusions (ALK,RET, andROS1) in 2.3%. Treatment‐induced resistance mutations were common in this cohort, including driver‐dependent and driver‐independent alterations. In the subset of patients who had progressive disease duringEGFRtherapy, 64% had known or putative resistance alterations detected in plasma. Subset analysis revealed that ctDNA increased the identification of driver mutations by 65% over standard‐of‐care, tissue‐based testing at diagnosis. A pooled data analysis on this plasma‐based assay demonstrated that targeted therapy response rates were equivalent to those reported from tissue analysis.

Conclusions

Comprehensive ctDNA analysis detected the presence of therapeutically targetable driver and resistance mutations at the frequencies and distributions predicted for the study population. These findings add support for comprehensive ctDNA testing in patients who are incompletely tested at the time of diagnosis and as a primary option at the time of progression on targeted therapies.
Early information needs of adolescents and young adults about late effects of cancer treatment
Authors: Greenzang Katie A. , Fasciano Karen M. , Block Susan D. , Mack Jennifer W.
Published: May 2020

Background

Adolescent and young adult (AYA) cancer survivors have high risks of late effects. Little is known about the late‐effect information needs of AYAs early in treatment or their role in treatment decision making. This study evaluated the importance, quality, and implications of information about late effects in AYAs recently diagnosed with cancer.

Methods

This study surveyed 201 AYAs with cancer who were 15 to 29 years old and were treated at the Dana‐Farber Cancer Institute (Boston, Massachusetts). Patients were approached within 6 weeks of their diagnosis and were asked about their late‐effect and infertility information needs, treatment decision making, and communication outcomes.

Results

Forty‐five percent of the participants were female; 88% were white. Most AYAs (87% [173 of 200]) considered information about the risks of late effects to be extremely or very important; 80% (159 of 200) valued information about infertility. Many were distressed by information about late effects (53% [105 of 200]) and infertility (45% [89 of 200]); those who considered late‐effect information distressing were more likely to value this information (P < .0001). Consideration of late effects (41% [82 of 201]) and infertility (36% [72 of 201]) greatly influenced many patients' treatment decision making. Although 92% of the patients (184 of 199) reported receiving high‐quality information about the diagnosis, 57% (113 of 199; P < .0001) and 65% (130 of 199; P < .0001) felt that they had received high‐quality information about late effects and infertility, respectively.

Conclusions

Most AYAs with cancer value early information about the risks of late effects and infertility, yet many patients felt that they had not received high‐quality information about these topics. The development of age‐appropriate late‐effect communication strategies that recognize high AYA distress may help to address the gap between desired information and perceived information quality.
Effects of Solid Electrolyte Interphase Components on the Reduction of LiFSI over Lithium Metal
Authors: Kamphaus Ethan P. , Gomez Stefany Angarita , Qin Xueping , Shao Minhua , Balbuena Perla B.
Published: May 2020

The use of a lithium metal anode still presents a challenging chemistry and engineering problem that holds back next generation lithium battery technology. One of the issues facing lithium metal is the presence of the solid electrolyte interphase (SEI) layer that forms on the electrode creating a variety of chemical species that change the properties of the electrode and is closely related to the formation and growth of lithium dendrites. In order to advance the scientific progress of lithium metal more must be understood about the fundamentals of the SEI. One property of the SEI that is particularly critical is the passivating behavior of the different SEI components. This property is critical to the continued formation of SEI and stability of the electrolyte and electrode. Here we report the investigation of the passivation behavior of Li2O, Li2CO3, LiF and LiOH with the lithium salt LiFSI. We used large computational chemistry models that are able to capture the lithium/SEI interface as well as the SEI/electrolyte interface. We determined that LiF and Li2CO3 are the most passivating of the SEI layers, followed by LiOH and Li2O. These results match previous studies of other Li salts and provide further examination of LiFSI reduction.
A Novel 3D Petal‐Like SnS2 Hierarchical Structure with Superior Photocatalytic Hydrogen Production Ability
Authors: Ding Yifan , Liu Shengqian , Li Jun , Qi Xiang
Published: May 2020

Herein, a novel 3D petal‐like SnS2 hierarchical structure is successfully prepared by a simple hydrothermal method. The as‐prepared samples are characterized by X‐ray diffraction and scanning electron microscopy. UV–vis spectra exhibit an absorption edge of ≈635 nm. Photoelectrochemical measurements demonstrate that the photocurrent density can be effectively increased from 0.04 to 1.10 μA cm−2 with applied bias potential range from 0.1 to 1.0 V. Additionally, there is no significant decay of photocurrent density after 60 cycles. Its remarkable performance and excellent stability in photocatalytic hydrogen evolution can be attributed to the huge specific surface area, unique hierarchical structure of petals, and high charge separation efficiency. Based on these results, a conclusion can be drawn that the novel 3D petal‐like SnS2 hierarchical structure will have a good development prospect in the future.
Layered Crystal Structural Entecavir Monohydrate: Prepared in Pure Water and Calculated by DFT
Authors: Kang Yanlei , Yu Dongdong , Miao Haoyu , Cheng Jianbo , Yu Xiaofeng , Zhou Jianguang
Published: May 2020

Entecavir (ETV) is approved by the Food and Drug Administration for the treatment of chronic hepatitis B in 2005. ETV monohydrate (ETV‐H) is used as drug substance in pharmaceutical industry. In this work, ETV‐H is prepared in pure water. The single crystal structure of ETV‐H is originally reported by Jiang and Liu in 2009 and shows a layered structure in ETV‐H crystal. Then ETV‐H is first studied by density functional theory method at B3LYP/6‐311+G(d,p) level. The optimized geometric parameters of ETV‐H agree well with the reported single crystal data and theoretical vibrational frequencies are consistent with experimental spectra. Molecular electronic potential and natural bond orbital results exhibit the molecular connection properties of the layered structure. The theoretical calculated dihedral angles between two ETV molecules are 177.6° and 176.8°, indicating that two ETV molecules are almost in the same plane. The theoretical calculated interlayer space is 16.4 Å, which is similar to the calculated interlayer space 16.7 Å using X‐ray diffraction result according to Bragg's law. These calculated results further illustrate the existence of the layered structure in ETV‐H crystal. This study may provide an idea for the future drug research.
EGFR‐targeted CAR‐T cells are potent and specific in suppressing triple‐negative breast cancer both in vitro and in vivo
Authors: Xia Lin , Zheng Zao‐zao , Liu Jun‐yi , Chen Yu‐jie , Ding Jian‐cheng , Xia Ning‐shao , Luo Wen‐xin , Liu Wen
Published: May 2020

Objectives

Triple‐negative breast cancer (TNBC) is well known for its strong invasiveness, rapid recurrence and poor prognosis. Immunotherapy, including chimeric antigen receptor‐modified T (CAR‐T) cells, has emerged as a promising tool to treat TNBC. The identification of a specific target tumor antigen and the design of an effective CAR are among the many challenges of CAR‐T therapy.

Methods

We reported that epidermal growth factor receptor (EGFR) is highly expressed in TNBC and consequently designed an optimal third generation of CAR targeting EGFR. The efficacy of primary T lymphocytes infected with EGFR CAR lentivirus (EGFR CAR‐T) against TNBC was evaluated both in vitro and in vivo. The signalling pathways activated in tumor and EGFR CAR‐T cells were revealed by RNA sequencing analysis.

Results

Third‐generation EGFR CAR‐T cells exerted potent and specific suppression of TNBC cell growth in vitro, whereas limited cytotoxicity was observed towards normal breast epithelial cells or oestrogen receptor‐positive breast cancer cells. This capability was further demonstrated in vivo in a xenograft mouse model, with minimal off‐tumor cytotoxicity. Mechanistically, in vitro stimulation with TNBC cells induced the expansion of naïve‐associated EGFR CAR‐T cells and enhanced their persistence. Furthermore, EGFR CAR‐T cells activated the interferon γ, granzyme–perforin–PARP and Fas–FADD–caspase signalling pathways in TNBC cells.

Conclusion

We demonstrate that EGFR is a relevant immunotherapeutic target in TNBC, and EGFR CAR‐T exhibits potent and specific antitumor activity against TNBC, suggesting the potential of this third‐generation EGFR CAR‐T as an immunotherapy tool to treat TNBC in the clinic.
A case of metastatic rectal adenocarcinoma diagnosed by thyroid cytology
Authors: Sakaleshpura Mallikarjunappa Subramanya , Valluru Neelima , Park Ji‐Weon , Gattuso Paolo , Cheng Lin
Published: May 2020

Fine‐needle aspiration (FNA) cytology of the thyroid gland has been widely used for the evaluation of thyroid nodules. Most of the nodules are primary thyroid lesions. However, up to 4% of thyroid FNA may harbor a metastatic neoplasm. The metastases are most commonly from lung, kidney, breast, and skin. Metastatic colorectal cancers are also seen in thyroid but less common. Here we report the cytologic features, differential diagnosis and clinical implications of a metastatic rectal adenocarcinoma to the thyroid gland diagnosed by FNA.
Ensuring identifiability in hierarchical mixed effects Bayesian models
Authors: Ogle Kiona , Barber Jarrett J.
Published: May 2020

Ecologists are increasingly familiar with Bayesian statistical modeling and its associated Markov chain Monte Carlo (MCMC) methodology to infer about or to discover interesting effects in data. The complexity of ecological data often suggests implementation of (statistical) models with a commensurately rich structure of effects, including crossed or nested (i.e., hierarchical or multi‐level) structures of fixed and/or random effects. Yet, our experience suggests that most ecologists are not familiar with subtle but important problems that often arise with such models and with their implementation in popular software. Of foremost consideration for us is the notion of effect identifiability, which generally concerns how well data, models, or implementation approaches inform about, i.e., identify, quantities of interest. In this paper, we focus on implementation pitfalls that potentially misinform subsequent inference, despite otherwise informative data and models. We illustrate the aforementioned issues using random effects regressions on synthetic data. We show how to diagnose identifiability issues and how to remediate these issues with model reparameterization and computational and/or coding practices in popular software, with a focus on JAGS, OpenBUGS, and Stan. We also show how these solutions can be extended to more complex models involving multiple groups of nested, crossed, additive, or multiplicative effects, for models involving random and/or fixed effects. Finally, we provide example code (JAGS/OpenBUGS and Stan) that practitioners can modify and use for their own applications.
FloraSNevada: a trait database of the vascular flora of Sierra Nevada, southeast Spain
Authors: Lorite Juan , Ros‐Candeira Andrea , Alcaraz‐Segura Domingo , Salazar‐Mendías Carlos
Published: May 2020

Providing a complete data set with species and trait information for a given area is essential for assessing plant conservation, management, and ecological restoration, for both local and global applications. Also, these data sets provide additional information for surveys or data collections, establishing the starting point for more detailed studies on plant evolution, vegetation dynamics, and vegetation responses to disturbance and management. This data base covers Sierra Nevada mountains (southeastern Spain), a recognized plant biodiversity hotspot within the Mediterranean context. According to previous available data (before this augmented compilation), these mountains host 7% of the 24,000 Mediterranean vascular plants, despite covering just 0.01% of its area. Another characteristic of the Sierra Nevada is the great singularity of its flora, with 95 taxa being endemic to the high‐mountain area of Sierra Nevada and surroundings. From these endemic taxa, 70% are endangered by different threats, global warming being a leading cause. We seek to provide a complete and updated database of the flora of the Sierra Nevada mountains (southeast Spain). The goal of the present data set is to compile the names of all the vascular plant taxa inhabiting Sierra Nevada, together with relevant features including taxonomical, morphological–ecological traits, distribution, habitats, abundance, and conservation status. The data were compiled according to all the available information sources on taxonomy, ecology, and plant‐species distribution. The resulting data set includes 2,348 taxa belonging to 1,937 species, 377 subspecies, and 34 hybrids, from a total of 756 genera and 146 families represented in the collection. For each taxa, together with taxonomical information (Phylum, Class, Family, Genus, Taxa), we compiled plant traits (life form, spinescence, flower symmetry, flower sexuality, plant gender, androecium:ginoecium ratio, flower color, perianth type, pollinator type, flowering, seed dispersal, and vegetative reproduction), and their environmental association (origin, endemic character, general distribution, substrate, elevation, habitat, local abundance, hygrophilous behavior, and conservation status). All these traits were compiled from all the available information sources, resulting in a complete and updated database for Sierra Nevada vascular flora. This data set provides valuable information on plant traits in an outstanding micro hotspot within the Mediterranean hotspot. This data set can be freely used for noncommercial purposes. This data set is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0). When you use this data set, we request that you cite the data and this data paper.
Magnetic Modification and the Mechanism of Tb‐Phthalocyanine Single Molecule Magnets Prepared by a High Yield Method
Authors: Ruan Liuxia , Tong Junwei , Qin Gaowu , Zhou Lianqun , Jiao Xuechen , Zhang Xianmin
Published: May 2020

Lanthanide single‐molecule magnets are the most promising materials to be applied in the future spintronics applications. In this report, we firstly synthesize double‐decker Phthalocyanines (Pc), TbPc2 single‐molecule magnets and paramagnetic YPc2 by a straightforward solvothermal route with a yield up to 16 %, which is three times larger than that of conventional method. Their crystal structures and properties are systematically characterized by the matrix‐assisted laser desorption ionization–time‐off light mass spectrometry, X‐ray diffractometer, Ultraviolet–visible spectra, Fourier transform infrared spectra, X‐ray photoemission spectroscopy, near‐edge X‐ray absorption fine structure (NEXAFS) spectroscopy, Inductive Coupled Plasma Emission Spectrometer and magnetic measurements. The NEXAFS spectroscopy confirms that a strong peak at 401 eV emerges not YPc2 but TbPc2, clearly indicating the different electronic structures of YPc2 and TbPc2. A typical hysteresis loop of single molecule magnet is observed for TbPc2. While, YPc2 shows a paramagnetic character. The SMM property of TbPc2 modified by introducing YPc2 was studied in detail. The maximum hysteresis area appears for the sample with Tb/Y = 7:3, which obviously demonstrates the concentration of YPc2 affects magnetic relaxation process by varying the intermolecular interactions of TbPc2. The barrier energy fitted from the results of alternating‐current magnetic susceptibility is 740 K for TbPc2 and 781 K for the sample with Tb/Y = 7:3, further indicating that the isolation of neighbor Tb ions by Y ions could slow down the flip of magnetic dipole.
Alkyne‐Monofunctionalized Gold Nanoparticles as Massive Molecular Building Blocks
Authors: Peters Erich Henrik , Mayor Marcel
Published: May 2020

Using a tripodal, thioether‐based ligand comprising a remote protected acetylene, we efficiently stabilize small gold nanoparticles (Ø ≈ 1.2 nm) which are isolated and purified by chromatography. The 1:1 ligand‐to‐particle ratio is obtained by comparing the particles' dimensions measured by transmission electron microscopy with the weight fraction of the coating ligand determined by thermogravimetric analysis. The single ligand coating of the gold particle guarantees the presence of a single masked alkyne per particle. It can be addressed by wet chemical protocols providing the particles with the properties of “massive molecules”. The “massive molecule” nature of the particles is demonstrated by involving them in wet chemical coupling protocols like oxidative acetylene coupling providing gold nanoparticle dimers (34 % isolated yield) or alkyne‐azide “click”‐chemistry with a suitable triazide, giving trimeric particle architectures (30 % determined by transmission electron microscopy). The particle stabilization obtained by the coating ligand allows, for the first time, to treat these multi‐particle architectures by size exclusion chromatography.
Elucidating the Role of Bifunctional Cobalt‐Manganese Catalyst Interactions for Higher Alcohol Synthesis
Authors: Paterson James , Partington Roy , Peacock Mark , Sullivan Kay , Wilson Jon , Xu Zhuoran
Published: May 2020

Catalyst promoters are often used to tune or improve performance with little understanding as to how they work. Here we present a fundamental evaluation of cobalt‐manganese interactions in Fischer‐Tropsch (FT) catalysis and evaluate a new bifunctional catalyst for CO dissociation and CO insertion mechanisms. FT has gained considerable attention recently due to the potential to convert bio or municipal waste feeds into commercial fuels and chemicals. Products are commonly highly linear paraffins, but here we show how the role of manganese can tune selectivity for linear olefins and alcohols in a copper, iron and alkali metal free cobalt bifunctional catalyst. These products also have significant commercial value for lubricants, plasticizers, detergents and base chemicals. Advanced catalyst characterization is shown with in situ techniques (XRD, EXAFS, PDF & TEM), while the FT products are fully analysed by NMR, GC and GCxGC. The role of manganese during catalyst synthesis is reviewed while fundamental understanding of the formation of a mixed metal oxide spinel is presented. The Co–Mn interactions change during catalyst reduction, with EXAFS showing cobalt metal and MnO as the main species present.