bluuebunny/crossref_metadata_2025 huggingface dataset:
Copper‐catalyzed Reaction of Anthranils with Methyl Ketones: Site‐Selective C5‐Dicarbonylation of Anthranils
Authors: Zhuang Shi‐Yi , Tang Yong‐Xing , He Cai , Chen Xiang‐Long , Xue Wei‐Jian , Wu Yan‐Dong , Wu An‐Xin
Published: December 2020

A copper‐catalyzed site‐selective C5‐dicarbonylation reaction of anthranils has been developed for synthesis of 1,2‐dicarbonyl compounds using methyl ketone as a commercially available carbonylation reagent. This process represents the first example to implement the C5‐dicarbonylation of anthranils, which involves an oxidative Csp3‐H/Csp2‐H cross‐coupling reaction along with thermolytic N−O bond cleavage.

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Synthetic Chemistry with Lewis Acidity‐Diminished B(aam) and B(dan) Groups: Borylation Reactions and Direct Cross‐Couplings
Authors: Kamio Shintaro , Yoshida Hiroto
Published: December 2020

This review describes recent advances in the synthesis of anthranilamide/1,8‐diaminonaphthalene‐substituted organoboron compounds with diminished boron Lewis acidity via catalytic B(aam)‐ and B(dan)‐installing borylation reactions, which have attracted growing attention especially in the last five years owing to their unique reactivity, regioselectivity, and the outstanding stability toward air and moisture of organoboron compounds obtained therefrom. Direct Suzuki–Miyaura cross‐couplings with R–B(aam)/B(dan), which were believed to be wholly unreactive until recently, are also discussed.

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The Role of Cycle Life on the Environmental Impact of Li6.4La3Zr1.4Ta0.6O12 based Solid‐State Batteries
Authors: Smith Lucy , Ibn‐Mohammed Taofeeq , Astudillo Dolores , Brown Solomon , Reaney Ian M. , Koh S. C. Lenny
Published: December 2020

This study compares the environmental impacts of a lithium‐ion battery (LiB), utilizing a lithium iron phosphate cathode, with a solid‐state battery (SSB) based on a Li6.4La3Zr1.4Ta0.6O12 garnet‐structured electrolyte. It uses a hybrid life cycle assessment (LCA), according to two functional units, delivery of 50 MJ of electrical energy and kg of battery, to expand the system boundary. The results of the process LCA indicate that the environmental impact of LiBs is lower than SSBs across most environmental impact categories. Conversely, the input–output upstream global warming potential (GWP) of the LiBs, calculated by hybrid LCA, is higher than that of the SSBs. Sensitivity analysis shows that the SSB cycle life must increase from 100 to 2800 to achieve a GWP impact lower than that of LiBs and therefore outperform LiBs in this environmental impact category. The study, therefore, demonstrates that research into SSBs must be accelerated to achieve a functional and safe battery technology with a reduced impact on the environment.
The impact of geographical positioning on agri‐food businesses' failure considering nonlinearities
Authors: Mate‐Sánchez‐Val Mariluz
Published: December 2020

This study applies spatial econometric techniques to evaluate the effect of external economic agents located in agri‐food business environments on the probability of those businesses failing. A logistic regression model that incorporates spatial interactions has been applied to the data. In addition, the article proposes an intermediate step in the modeling process based on generalized additive models to determine the specific functional relationships between the probit model and the explanatory variables. The results reveal that geographic location has a significant effect on the probability that agri‐food companies fail to find significant nonlinearities. [EconLit Citations: G33, Q14, R10]
Difference between carbohydrate antigen 19‐9 and fluorine‐18 fluorodeoxyglucose positron emission tomography in evaluating the treatment efficacy of neoadjuvant treatment in patients with resectable and borderline resectable pancreatic ductal adenocarcinoma: Results of a dual‐center study
Authors: Akita Hirofumi , Takahashi Hidenori , Eguchi Hidetoshi , Asukai Kei , Hasegawa Shinichiro , Wada Hiroshi , Iwagami Yoshifumi , Yamada Daisaku , Tomimaru Yoshito , Noda Takehiro , Gotoh Kunihito , Kobayashi Shogo , Doki Yuichiro , Sakon Masato
Published: December 2020

Background

An accurate evaluation of neoadjuvant treatment is important to maximize the prognostic benefit of this strategy in each individual patient. The main aim of the present study is to investigate the difference between carbohydrate antigen 19‐9 and fluorine‐18 fluorodeoxyglucose positron emission tomography (FDG‐PET) in evaluating the response to neoadjuvant treatment for resectable and borderline resectable pancreatic ductal adenocarcinoma (PDAC) patients.

Methods

Pancreatic ductal adenocarcinoma patients with positive standard uptake values (SUV) on FDG‐PET before neoadjuvant chemoradiotherapy (NACRT) were enrolled (n = 141). In all patients, CA19‐9 and FDG‐PET were evaluated before the initiation of and after the completion of NACRT. The statuses of CA19‐9 and FDG uptake alterations during NACRT were assessed in association with survival and tumor recurrence profiles.

Results

A favorable response in each CA19‐9 and FDG‐PET was significantly related to better survival, respectively, than the unfavorable response (44.3% vs 19.5%, P < .001 and 45.8% vs 24.6%, P < .001). The status of CA19‐9 was significantly associated with the incidence of distant recurrence whereas the status of FDG‐PET was significantly associated with the incidence of local recurrence, and only patients with a favorable response in both CA19‐9 and PET statuses showed a significantly better survival than the others (5‐year survival: 56% vs 24%, P < .001), and those with unfavorable response in either of CA19‐9 or PET status showed similar poor survival to those with unfavorable in both (P = .164).

Conclusion

CA19‐9 and PET evaluation provided oncologically different risk assessments in terms of tumor recurrence profile, and favorable response in both CA19‐9 and FDG‐PET were necessary to achieve prognostic benefit from NACRT.
Brain‐Inspired Synaptic Resistor Circuits for Self‐Programming Intelligent Systems
Authors: Chen Yong
Published: December 2020

Unlike artificial intelligent systems based on computers, which need to be preprogrammed for specific tasks, restricting their functions to their preprogrammed ranges, the human brain does not need to be preprogrammed, and has general intelligence to create new tactics in complex and erratic environments. The basic element in the brain, a synapse, has the function to process and learn from signals in real time by following Hebb's rule, which is a critical function missing from the transistor, the basic device in computers. In this work, a computing circuit based on synaptic resistors (synstors) with signal processing and Hebbian learning functions is modeled and analyzed. A synstor circuit emulates a neurobiological network to concurrently execute signal processing and learning algorithms in parallel mode, does not need to be preprogrammed, and has the capability to optimize and create new algorithms in complex and erratic environments with speed and energy efficiency significantly superior to those of existing computing circuits. The synstor circuit can potentially circumvent the fundamental limitations of existing computing circuits, leading to a new computing platform with real‐time self‐programming functionality and general intelligence in complex and erratic environments.
Implementing long‐term baselines into primate tool‐use studies
Authors: Bandini Elisa
Published: December 2020

Studies on primate tool‐use often involve the use of baseline conditions, as they allow for the examination of any differences in the subjects' behavior before and after the introduction of a tool‐use task. While these baseline conditions can be powerful for identifying the relative contributions of individual and social learning for the acquisition of tool‐use behaviors in naïve (usually captive) subjects, many have criticized them for being too short, and not allowing enough time for the behavior to develop spontaneously. Furthermore, some wild tool‐use behaviors such as chimpanzee nut‐cracking require animals to manipulate and familiarize themselves with the materials of the behavior within a “sensitive learning period” before it develops later on in life. One solution to this problem is to implement long‐term baselines, in which, with collaboration with zoological institutions, the materials of the behavior are left in the enclosure for an extended period. The keepers would then be asked not to demonstrate or train the animals in the target behavior, but to report back to the researchers if they observe the behavior emerge during this extended period. Alongside keeper reports, video cameras could be installed in the enclosure to minimize the chance of false negatives and to allow for coding and inter‐rater reliability to be carried out on the videos. These long‐term baselines therefore provide extended enrichment opportunities for the animals, alongside allowing the zoological institution to publicize their involvement with the study and guests to observe animals interacting with different testing apparatuses and tools. Finally, long‐term baselines can provide invaluable insight on the individual and social learning abilities of primates as well as the potential development stages and sensitive learning periods required for specific behaviors.
Endogenous antagonists of N‐methyl‐d‐aspartate receptor in schizophrenia
Authors: Jorratt Pascal , Hoschl Cyril , Ovsepian Saak V.
Published: December 2020

Schizophrenia is a chronic neuropsychiatric brain disorder that has devastating personal impact and rising healthcare costs. Dysregulation of glutamatergic neurotransmission has been implicated in the pathobiology of the disease, attributed largely to the hypofunction of the N‐methyl‐d‐aspartate (NMDA) receptor. Currently, there is a major gap in mechanistic analysis as to how endogenous modulators of the NMDA receptors contribute to the onset and progression of the disease. We present a systematic review of the neurobiology and the role of endogenous NMDA receptor antagonists in animal models of schizophrenia, and in patients. We discuss their neurochemical origin, release from neurons and glia with action mechanisms, and functional effects, which might contribute toward the impairment of neuronal processes underlying this complex pathological state. We consider clinical evidence suggesting dysregulations of endogenous NMDA receptor in schizophrenia, and highlight the pressing need in future studies and emerging directions, to restore the NMDA receptor functions for therapeutic benefits.
Selective Oxidation of Anilines to Azobenzenes and Azoxybenzenes by a Molecular Mo Oxide Catalyst
Authors: Han Sheng , Cheng Ying , Liu Shanshan , Tao Chaofu , Wang Aiping , Wei Wanguo , Yu Han , Wei Yongge
Published: December 2020

Aromatic azo compounds, which play an important role in pharmaceutical and industrial applications, still face great challenges in synthesis. Herein, we report a molybdenum oxide compound, [N(C4H9)4]2[Mo6O19] (1), catalyzed selective oxidation of anilines with hydrogen peroxide as green oxidant. The oxidation of anilines can be realized in a fully selectively fashion to afford various symmetric/asymmetric azobenzene and azoxybenzene compounds, respectively, by changing additive and solvent, avoiding the use of stoichiometric metal oxidants. Preliminary mechanistic investigations suggest the intermediacy of highly active reactive and elusive Mo imido complexes.
A Broad‐Spectrum Catalytic Amidation of Sulfonyl Fluorides and Fluorosulfates**
Authors: Wei Mingjie , Liang Dacheng , Cao Xiaohui , Luo Wenjun , Ma Guojian , Liu Zeyuan , Li Le
Published: December 2020

A broad‐spectrum, catalytic method has been developed for the synthesis of sulfonamides and sulfamates. With the activation by the combination of a catalytic amount of 1‐hydroxybenzotriazole (HOBt) and silicon additives, amidations of sulfonyl fluorides and fluorosulfates proceeded smoothly and excellent yields were generally obtained (87–99 %). Noticeably, this protocol is particularly efficient for sterically hindered substrates. Catalyst loading is generally low and only 0.02 mol % of catalyst is required for the multidecagram‐scale synthesis of an amantadine derivative. In addition, the potential of this method in medicinal chemistry has been demonstrated by the synthesis of the marketed drug Fedratinib via a key intermediate sulfonyl fluoride 13. Since a large number of amines are commercially available, this route provides a facile entry to access Fedratinib analogues for biological screening.
Self‐Pillared Ultramicroporous Carbon Nanoplates for Selective Separation of CH4/N2
Authors: Xu Shuang , Li Wen‐Cui , Wang Cheng‐Tong , Tang Lei , Hao Guang‐Ping , Lu An‐Hui
Published: December 2020

There is growing evidence that pillaring up a densely packed ultramicroporous two‐dimensional (2D) structure is an effective strategy to reduce their internal diffusion. Reliable pillaring paradigms, however, is rather challenging. Here we report a one‐pot multi‐component sequential assembly method for the preparation of a new self‐pillared 2D polymer and ultramicroporous carbon with integrated surface protrusions. The molecular level pillaring process is surprisingly fast, that is, in 10 min. The thickness of nanoplate edge and the density (roughness), angle as well as height of protrusions can be precisely tuned. Exemplified in coal bed methane purification/separation, this unique pillared 2D carbons exhibit a CH4/N2 selectivity up to 24 at a low CH4 partial pressure and two orders of magnitude faster CH4 diffusion kinetics than the commercial carbon molecular sieves. This solution synthesis methodology is generalizable for creation and fine tuning of pillared 2D heterostructures.
Scan and Unlock: A Programmable DNA Molecular Automaton for Cell‐Selective Activation of Ligand‐Based Signaling
Authors: Zhang Jinghui , Qiu Zongyang , Fan Jiahui , He Fang , Kang Wenyuan , Yang Sihui , Wang Hong‐Hui , Huang Jing , Nie Zhou
Published: December 2020

Selective modulation of ligand–receptor interaction is essential in targeted therapy. In this study, we design an intelligent “scan and unlock” DNA automaton (SUDA) system to equip a native protein‐ligand with cell‐identity recognition and receptor‐mediated signaling in a cell‐type‐specific manner. Using embedded DNA‐based chemical reaction networks (CRNs) on the cell surface, SUDA scans and evaluates molecular profiles of cell‐surface proteins via Boolean logic circuits. Therefore, it achieves cell‐specific signal modulation by quickly unlocking the protein‐ligand in proximity to the target cell‐surface to activate its cognate receptor. As a proof of concept, we non‐genetically engineered hepatic growth factor (HGF) with distinct logic SUDAs to elicit target cell‐specific HGF signaling and wound healing behaviors in multiple heterogeneous cell types. Furthermore, the versatility of the SUDA strategy was shown by engineering tumor necrotic factor‐α (TNFα) to induce programmed cell death of target cell subpopulations through cell‐specific modulation of TNFR1 signaling.
Cocrystal Engineering: Toward Solution‐Processed Near‐Infrared 2D Organic Cocrystals for Broadband Photodetection
Authors: Wang Yu , Wu Huang , Zhu Weigang , Zhang Xiaotao , Liu Zheyuan , Wu Yishi , Feng Changfu , Dang Yanfeng , Dong Huanli , Fu Hongbing , Hu Wenping
Published: December 2020

Large‐area 2D cocrystals with strong near‐infrared (NIR) absorption have been designed and prepared. Driven by the intermolecular charge‐transfer (CT) interactions, zinc tetraphenylporphyrin (donor) and C60 (acceptor) self‐assemble into a NIR cocrystal with absorption wavelength up to 1080 nm. By tailoring the growth solvents and processes, the cocrystal morphologies can be tuned from 1D nanowires, 2D nanosheets to large‐area 2D cocrystal films with length reaching several millimeters. Owing to the highly ordered donor–acceptor arrangement, the CT absorption in the 2D cocrystals is enhanced and is comparable to singlet absorption. The uniform 2D cocrystals, with enhanced CT absorption in the NIR region, displays a high responsivity of 2424 mA W−1 to NIR light and a fast response time of 0.6 s. The excellent device performance is attributed to the generation of long‐lived free charge carriers as revealed by transient absorption spectroscopy and optimization of device configuration.
Octagon‐Embedded Carbohelicene as a Chiral Motif for Circularly Polarized Luminescence Emission of Saddle‐Helix Nanographenes
Authors: Medel Miguel A. , Tapia Rubén , Blanco Victor , Miguel Delia , Morcillo Sara P. , Campaña Araceli G.
Published: December 2020

We report a new family of hexa‐peri‐hexabenzocoronene (HBC)‐based helical nanographenes incorporating π‐extended carbo[5]helicenes bearing an octagonal carbocycle. This family represents a new kind of highly distorted saddle‐helix hybrid nanographenes. For the first time, the eight‐membered ring becomes a constituent of both a carbo[5]helicene and a HBC and thus, the negative curvature is responsible for twisting both units. This novel chiral motif, namely, oct‐[5]helicene results in the largest torsion angle recorded so far for a carbo[5]helicene (θ=79.5°), as it has been suggested by DFT‐calculations and confirmed by X‐ray crystallography. Consequently, the barriers of isomerization become exceptionally high for a [5]helicene unsubstituted in the fjord region since neither racemization nor decomposition were observed at 200 °C for 1 or 3 during 5 h. Therefore, racemic resolutions allowed subsequent chiroptical studies showing the ECD and CPL responses of this novel family of chiral nanographenes.
Surface Functionalization of Black Phosphorus with Nitrenes: Identification of P=N Bonds by Using Isotopic Labeling
Authors: Walz Mitra Kendahl L. , Chang Christine H. , Hanrahan Michael P. , Yang Jiaying , Tofan Daniel , Holden William M. , Govind Niranjan , Seidler Gerald T. , Rossini Aaron J. , Velian Alexandra
Published: December 2020

Surface functionalization of two‐dimensional crystals is a key path to tuning their intrinsic physical and chemical properties. However, synthetic protocols and experimental strategies to directly probe chemical bonding in modified surfaces are scarce. Introduced herein is a mild, surface‐specific protocol for the surface functionalization of few‐layer black phosphorus nanosheets using a family of photolytically generated nitrenes (RN) from the corresponding azides. By embedding spectroscopic tags in the organic backbone, a multitude of characterization techniques are employed to investigate in detail the chemical structure of the modified nanosheets, including vibrational, X‐ray photoelectron, solid state31P NMR, and UV‐vis spectroscopy. To directly probe the functional groups introduced on the surface, R fragments were selected such that in conjunction with vibrational spectroscopy,15N‐labeling experiments, and DFT methods, diagnostic P=N vibrational modes indicative of iminophosphorane units on the nanosheet surface could be conclusively identified.
Two‐Dimensional Porous Molybdenum Phosphide/Nitride Heterojunction Nanosheets for pH‐Universal Hydrogen Evolution Reaction
Authors: Gu Ying , Wu Aiping , Jiao Yanqing , Zheng Huiru , Wang Xueqi , Xie Ying , Wang Lei , Tian Chungui , Fu Honggang
Published: December 2020

Herein, we present a new strategy for the synthesis of 2D porous MoP/Mo2N heterojunction nanosheets based on the pyrolysis of 2D [PMo12O40]3−‐melamine (PMo12‐MA) nanosheet precursor from a polyethylene glycol (PEG)‐mediated assembly route. The heterostructure nanosheets are ca. 20 nm thick and have plentiful pores (<5 nm). These structure features offer advantages to promote the HER activity, including the favorable water dissociation kinetics around heterojunction as confirmed by theoretical calculations, large accessible surface of 2D nanosheets, and enhanced mass‐transport ability by pores. Consequently, the 2D porous MoP/Mo2N heterojunction nanosheets exhibit excellent HER activity with low overpotentials of 89, 91 and 89 mV to achieve a current density of 10 mA cm−2 in alkaline, neutral and acidic electrolytes, respectively. The HER performance is superior to the commercial Pt/C at a current density >55 mA cm−2 in neutral medium and >190 mA cm−2 in alkaline medium.
Donor/Acceptor Pairs Created by Electrostatic Interaction: Design, Synthesis, and Investigation on the Exciplex Formed Within the Pair
Authors: He Lei , Bai Rubing , Yu Renyou , Meng Xianwen , Tian Mingxing , Wang Xiaoxiang
Published: December 2020

Exciplexes formed between donors and acceptors have been widely explored but isolating them from each other and tuning the interaction between the donor and acceptor have remained challenges. Here, we report donor/acceptor (D/A) pairs created by electrostatic interaction between a carbazole‐based anionic donor and a 1,3,5‐triazine‐based cationic acceptor and the exciplex formed within the pair. In a diluted film, the D/A pair affords an isolated exciplex which shows thermally activated delayed fluorescence (TADF). By changing the anchoring position of the imidazolium cation in the cationic acceptor, interactions between the donor and acceptor can be changed. Compared to the conventional exciplex formed in a neat film, the isolated exciplex exhibits a substantially higher luminescence efficiency. The D/A pairs show intriguing mechanochromic luminescence and mechanical grinding‐induced/reinforced TADF in the solid state and promising performances as emitters in organic light‐emitting diodes.
Rhodium‐Catalyzed Enantioselective Synthesis of β‐Amino Alcohols via Desymmetrization of gem‐Dimethyl Groups
Authors: Liu Bingxian , Xie Pengfei , Zhao Jie , Wang Juanjuan , Wang Manman , Jiang Yuqin , Chang Junbiao , Li Xingwei
Published: December 2020

Desymmetrization of gem‐dimethyl groups en route to the rhodium(III)‐catalyzed enantioselective sp3 C−H amidation is reported. Synthetically important β‐amino alcohol derivatives were accessed in moderate to good yields and high enantioselectivity. The high enantioselectivity is enabled by an appropriate oxime directing group, sterically biased gem‐groups in the C−H substrate, and high reactivity of the amidating reagent.
Enriching Structural Diversity of Alkynyl‐Protected Gold Nanoclusters with Chlorides
Authors: Li Jiao‐Jiao , Guan Zong‐Jie , Yuan Shang‐Fu , Hu Feng , Wang Quan‐Ming
Published: December 2020

The synthesis and isolation of alkynyl/chloride‐protected gold nanoclusters is described. Silica gel column chromatography is effective in isolating gold nanoclusters from the as‐synthesized cluster mixture to give the clusters Na[Au25L18] (Au25), [HNEt3]3[Au67L32Cl4] (Au67), [HNEt3]4[Au106L40Cl12] (Au106), L=3,5‐bis(trifluoromethyl)‐phenylacetylide. Au67 and Au106 are new clusters; the structures were determined by X‐ray single‐crystal diffraction. Au67 contains a distorted Au18 Marks decahedron shelled by an irregular Au32 and further protected with two V‐shaped Au2L3, 13 linear AuL2 staples and 4 chlorides. Au67 is the first structurally determined 34e superatomic gold nanocluster. Au106 is composed of 106 Au atoms co‐protected by alkynyls and chlorides. It has a Au79 kernel, like in Au102(p‐MBA)44. The surface structure of Au106 includes 20 linear Au‐alkynyl staples, 5 Cl‐Au‐Cl and 2 Cl‐Au motifs. These three gold nanoclusters show size‐dependent electrochemical properties.
Tellurium(II)/Tellurium(III)‐Catalyzed Cross‐Dehydrogenative C−N Bond Formation
Authors: Cremer Christopher , Goswami Monalisa , Rank Christian K. , de Bruin Bas , Patureau Frederic W.
Published: December 2020

The TeII/TeIII‐catalyzed dehydrogenative C−H phenothiazination of challenging phenols featuring electron‐withdrawing substituents under mild aerobic conditions and with high yields is described. These unexpected TeII/TeIII radical catalytic properties were characterized by cyclic voltammetry, EPR spectroscopy, kinetic experiments, and DFT calculations.
3D Modeling of craniofacial ontogeny and sexual dimorphism in children
Authors: Smith Olivia A. M. , Nashed Youssef S. G. , Duncan Christian , Pears Nick , Profico Antonio , O'Higgins Paul
Published: December 2020

Background

The range of normal variation of growth and development of the craniofacial region is of direct clinical interest but incompletely understood. Here we develop a statistical model of craniofacial growth and development to compare craniofacial ontogeny between age groups and sexes and pilot an approach to modeling that is relatively straightforward to apply in the context of clinical research and assessment.

Methods

The sample comprises head surface meshes captured using a 3dMD five‐camera system from 65 males and 47 females (range 3–20 years) from the Headspace project, Liverpool, UK. The surface meshes were parameterized using 16 anatomical landmarks and 59 semilandmarks on curves and surfaces. Modes and degrees of growth and development were assessed and compared among ages and sexes using Procrustes based geometric morphometric methods.

Results

Regression analyses indicate that 3–10 year olds undergo greater changes than 11–20 year olds and that craniofacial growth and development differs between these age groups. The analyses indicate that males extend growth allometrically into larger size ranges, contributing substantially to adult dimorphism. Comparisons of ontogenetic trajectories between sexes find no significant differences, yet when hypermorphosis is accounted for in the older age group there is a significant residual sexual dimorphism.

Conclusions

The study adds to knowledge of how adult craniofacial form and sexual dimorphism develop. It was carried out using readily available software which facilitates replication of this work in diverse populations to underpin clinical assessment of deformity and the outcomes of corrective interventions.
Some effects of praise during the escape condition of the functional analysis
Authors: Weyman Jennifer R. , Bloom Sarah E. , Campos Claudia , Garcia Anna R.
Published: December 2020

Many researchers provide praise for complying with demands during the escape condition of the functional analysis (FA). However, praise may function as a reinforcer for some individuals which may reduce the aversiveness of task presentation or increase behavior that competes with problem behavior (e.g., compliance with demands). In general, this may result in lower or less stable levels of problem behavior and decrease the efficiency of the FA. Thus, the purpose of the current study was to evaluate some effects of praise on the rate of problem behavior and compliance during the escape condition of the FA in children diagnosed with autism spectrum disorder. We found that praise did not affect the rate of problem behavior but did increase compliance in three of five subjects. The results of the study and implications for the assessment of problem behavior are discussed.
Balancing glucose and oxygen uptake rates to enable high amorpha‐4,11‐diene production in Escherichia coli via the methylerythritol phosphate pathway
Authors: Patil Vikas , Santos Christine N. S. , Ajikumar Parayil K. , Sarria Stephen , Takors Ralf
Published: December 2020

Amorpha‐4,11‐diene (AMD4,11) is a precursor to artemisinin, a potent antimalarial drug that is traditionally extracted from the shrubs of Artemisia annua. Despite significant prior efforts to produce artemisinin and its precursors through biotechnology, there remains a dire need for more efficient biosynthetic routes for its production. Here, we describe the optimization of key process conditions for an Escherichia coli strain producing AMD4,11 via the native methylerythritol phosphate (MEP) pathway. By studying the interplay between glucose uptake rates and oxygen demand, we were able to identify optimal conditions for increasing carbon flux through the MEP pathway by manipulating the availability of NADPH required for terpenoid production. Installation of an optimal qO2/qglucose led to a 6.7‐fold increase in product titers and a 6.5‐fold increase in carbon yield.
Monitoring of Cell‐Dependent Reduced States Using Aptamer‐Functionalized Reduction‐Sensitive Quantum Dots
Authors: Lee Gwan‐Ho , Kang Sung Muk , Lee Soo Bin , Lee Dohyun , Ko Youngkuk , Nam Jungyeon , Jo Juhyun , Hah Sang Soo
Published: December 2020

Conjugation of quantum dot (QD) with oxidized nile blue (NB) is known to be able to strongly decrease fluorescence intensity of QD. In the present study, NB‐conjugated QD (QD‐NB) was functionalized with anti‐human epidermal growth factor receptor 2 aptamer to form aptamer‐functionalized QD‐NB (Apt‐QD‐NB), as a new biosensing platform to monitor aptamer‐dependent internalizations and reduction‐dependent transformations. Our study shows that more QD fluorescence signals in cells can be induced by the specific internalization of higher amounts of Apt‐QD‐NB and that the higher ratio of reduced NB over oxidized NB resulting from the different reducing environment of the cells can lead to brighter QD signals. Apt‐QD‐NBs are expected to be used as optical labels that can monitor intracellular metabolic pathways at the single‐cell level, because the use of Apt‐QD‐NBs to investigate drug effectiveness and cellular redox conditions offers exciting opportunities for drug screening.
The influence of social support in the rehabilitation of acid attack victims: A qualitative inquiry
Authors: Mittal Shalini , Singh Tushar , Verma Sunil K.
Published: December 2020

Acid attack refers to the act of hurling acid or any other corrosive substance on a person with the intention of injuring, harming, maiming, disfiguring or killing. Despite the fact that the number of acid attack cases in India have been rising, a separate section for acid attacks was not included in the Indian Penal Code until the year 2013. Even after the inclusion of this crime in the Indian Penal Code, the discourse about the crime and the condition of victims in the aftermath of the crime remains largely incomplete due to the selective focus on the medical treatment of the victims and punishment for the offenders. Therefore, the present paper attempts to explore social isolation as a consequence of the crime and the role of social support in the psychological rehabilitation of acid attack victims. The present research involved narrative interviews of a homogenous purposive sample of 30 female acid attack victims which were analysed using thematic content analysis. The findings suggest that victims of acid attack experience non‐social support in the form of social isolation social exclusion as a consequence of acid attack in addition to the lack of informational and instrumental social support. Results also suggest that social support plays a crucial role in the coping process of the acid attack victims. The insights of the present research will help in improving the understanding of the psychosocial correlates of acid attack victims and the recovery process of the acid attack victims.
Did judge dismiss coach's due process claim?
Authors: Lyerly Eric
Published: December 2020

T he plaintiff was the head coach of the Mohawk Valley Community College women's basketball team. At some point during the 2017–18 basketball season, the MVCC human resources director received an anonymous tip claiming the plaintiff had improperly loaned money to a student‐athlete in violation of National Junior College Athletic Association rules.
Success during crisis requires flexibility, adaptability
Authors: McCarthy Claudine
Published: December 2020

As Ken Kavanagh, Director of Athletics at Florida Gulf Coast University, looked out his office window on an October day, he watched the baseball team practicing in 80‐degree weather while wearing masks.
Spin State Tunes Oxygen Atom Transfer towards FeIVO Formation in FeII Complexes
Authors: Castillo Carmen E. , Gamba Ilaria , Vicens Laia , Clémancey Martin , Latour Jean‐Marc , Costas Miquel , Basallote Manuel G.
Published: December 2020

Oxoiron(IV) complexes bearing tetradentate ligands have been extensively studied as models for the active oxidants in non‐heme iron‐dependent enzymes. These species are commonly generated by oxidation of their ferrous precursors. The mechanisms of these reactions have seldom been investigated. In this work, the reaction kinetics of complexes [FeII(CH3CN)2L](SbF6)2 ([1](SbF6)2 and [2](SbF6)2) and [FeII(CF3SO3)2L] ([1](OTf)2 and [2](OTf)2 (1, L=Me,HPytacn; 2, L=nP,HPytacn; R,R′Pytacn=1‐[(6‐R′‐2‐pyridyl)methyl]‐4,7‐ di‐R‐1,4,7‐triazacyclononane) with Bu4NIO4 to form the corresponding [FeIV(O)(CH3CN)L]2+ (3, L=Me,HPytacn; 4, L=nP,HPytacn) species was studied in acetonitrile/acetone at low temperatures. The reactions occur in a single kinetic step with activation parameters independent of the nature of the anion and similar to those obtained for the substitution reaction with Cl− as entering ligand, which indicates that formation of [FeIV(O)(CH3CN)L]2+ is kinetically controlled by substitution in the starting complex to form [FeII(IO4)(CH3CN)L]+ intermediates that are converted rapidly to oxo complexes 3 and 4. The kinetics of the reaction is strongly dependent on the spin state of the starting complex. A detailed analysis of the magnetic susceptibility and kinetic data for the triflate complexes reveals that the experimental values of the activation parameters for both complexes are the result of partial compensation of the contributions from the thermodynamic parameters for the spin‐crossover equilibrium and the activation parameters for substitution. The observation of these opposite and compensating effects by modifying the steric hindrance at the ligand illustrates so far unconsidered factors governing the mechanism of oxygen atom transfer leading to high‐valent iron oxo species.
Cellular Fucosylation Inhibitors Based on Fluorinated Fucose‐1‐phosphates**
Authors: Pijnenborg Johan F. A. , Visser Eline A. , Noga Marek , Rossing Emiel , Veizaj Raisa , Lefeber Dirk J. , Büll Christian , Boltje Thomas J.
Published: December 2020

Fucosylation of glycans impacts a myriad of physiological and pathological processes. Inhibition of fucose expression emerges as a potential therapeutic avenue for example in cancer, inflammation, and infection. In this study, we found that protected 2‐fluorofucose 1‐phosphate efficiently inhibits cellular fucosylation with a four to seven times higher potency than known inhibitor 2FF, independently of the anomeric stereochemistry. Nucleotide sugar analysis revealed that both the α‐ and β‐GDP‐2FF anomers are formed inside the cell. In conclusion, we developed A2FF1P and B2FF1P as potent new tools for studying the role of fucosylation in health and disease and they are potential therapeutic candidates.
2D Ising Model for Adsorption‐induced Enantiopurification of Racemates
Authors: Dutta Soham , Yun Yongju , Widom Michael , Gellman Andrew J.
Published: December 2020

Mechanisms for the spontaneous transformation of achiral chemical systems into states of enantiomeric purity have important ramifications in modern pharmacology and potential relevance to the origins of homochirality in life on Earth. Such mechanisms for enantiopurification are needed for production of chiral pharmaceuticals and other bioactive compounds. Previously proposed chemical mechanisms leading from achiral systems to near homochirality are initiated by a symmetry‐breaking step resulting in a minor excess of one enantiomer via statistical fluctuations in enantiomer concentrations. Subsequent irreversible processes then amplify the majority enantiomer concentration while simultaneously suppressing minority enantiomer production. Herein, equilibrium adsorption of amino acid enantiomer mixtures onto chiral and achiral surfaces reveals amplification of surface enantiomeric excess relative to the gas phase; i. e. enantiopurification of chiral adsorbates by adsorption. This adsorption‐induced amplification of enantiomeric excess is shown to be well‐describe by the 2D Ising model. More importantly, the 2D‐Ising model predicts formation of homochiral monolayers from adsorption of racemic mixtures or prochiral molecules on achiral surfaces; i. e. enantiopurification with no apparent chiral driving force.
Pro‐inflammatory dopamine‐2 receptor‐specific T cells in paediatric movement and psychiatric disorders
Authors: Pilli Deepti , Zou Alicia , Dawes Ruebena , Lopez Joseph A , Tea Fiona , Liyanage Ganesha , Lee Fiona XZ , Merheb Vera , Houston Samuel D , Pillay Aleha , Jones Hannah F , Ramanathan Sudarshini , Mohammad Shekeeb , Kelleher Anthony D , Alexander Stephen I , Dale Russell C , Brilot Fabienne
Published: December 2020

Objectives

A dysregulated inflammatory response against the dopamine‐2 receptor (D2R) has been implicated in movement and psychiatric disorders. D2R antibodies were previously reported in a subset of these patients; however, the role of T cells in these disorders remains unknown. Our objective was to identify and characterise pro‐inflammatory D2R‐specific T cells in movement and psychiatric disorders.

Methods

Blood from paediatric patients with movement and psychiatric disorders of suspected autoimmune and neurodevelopmental aetiology (n = 24) and controls (n = 16) was cultured in vitro with a human D2R peptide library, and D2R‐specific T cells were identified by flow cytometric quantification of CD4+CD25+CD134+ T cells. Cytokine secretion was analysed using a cytometric bead array and ELISA. HLA genotypes were examined in D2R‐specific T‐cell‐positive patients. D2R antibody seropositivity was determined using a flow cytometry live cell‐based assay.

Results

Three immunodominant regions of D2R, amino acid (aa)121–131, aa171–181 and aa396–416, specifically activated CD4+ T cells in 8/24 patients. Peptides corresponding to these regions were predicted to bind with high affinity to the HLA of the eight positive patients and had also elicited the secretion of pro‐inflammatory cytokines IL‐2, IFN‐ γ, TNF, IL‐6, IL‐17A and IL‐17F. All eight patients were seronegative for D2R antibodies.

Conclusion

Autoreactive D2R‐specific T cells and a pro‐inflammatory Th1 and Th17 cytokine profile characterise a subset of paediatric patients with movement and psychiatric disorders, further underpinning the theory of immune dysregulation in these disorders. These findings offer new perspectives into the neuroinflammatory mechanisms of movement and psychiatric disorders and can influence patient diagnosis and treatment.
Development of a 43 color panel for the characterization of conventional and unconventional T‐cell subsets, B cells, NK cells, monocytes, dendritic cells, and innate lymphoid cells using spectral flow cytometry
Authors: Sahir Fairooz , Mateo Jericha Miles , Steinhoff Martin , Siveen Kodappully Sivaraman
Published: December 2020

Although many flow cytometers can analyze 30–50 parameters, it is still challenging to develop a 40+ color panel for the phenotyping of immune cells using fluorochrome conjugated antibodies due to limitations in the availability of spectrally unique fluorochromes that can be excited by the commonly used laser lines (UV, Violet, Blue, Green/Yellow‐green, and Red). Spectral flowcytometry is capable of differentiating fluorochromes with significant overlap in the emission spectra, enabling the use of spectrally similar fluorochrome pairs such as Brilliant Blue 515 and FITC in a single panel. We have developed a 43 color panel to characterize most of the immune subsets within the peripheral immune system, including conventional T cells, unconventional T cells such as invariant natural killer T cells (iNKT), Gamma delta (γδ) T‐cell subsets (TCR Vδ2, TCR Vγ9) and mucosal‐associated invariant T cells (MAIT), B‐cell subsets, natural killer (NK) cells, plasmacytoid dendritic cells, dendritic cell subsets, hematopoietic progenitor cells, basophils, and innate lymphoid cell (ILC) subsets (CD117, CRTH2). The panel includes surface markers to analyze activation (CD38, HLA‐DR, ICOS/CD278), differentiation (CD45RA, CD27, CD28, CD57), expression of cytokine and chemokine receptors (CD25, CD127, CCR10, CCR6, CCR4, CXCR3, CXCR5, CRTH2/CD294), and co‐inhibitory molecules and exhaustion (PD‐1, CD223/LAG‐3, TIGIT), which enables a deep characterization of PBMCs from peripheral blood. Cells were analyzed on a 5‐laser Cytek Aurora and data analysis was done using FlowJo. This panel can help to make a thorough interpretation of immune system, specifically when specimen quantity is low. The panel has not been completely optimized but would rather act as a guide toward the development of a workflow for optimized multicolor immunophenotyping panel.
Early use of remote dielectric sensing after hospitalization to reduce heart failure readmissions
Authors: Lala Anuradha , Barghash Maya H. , Giustino Gennaro , Alvarez‐Garcia Jesus , Konje Swiri , Parikh Aditya , Ullman Jennifer , Keith Brendan , Donehey John , Mitter Sumeet S. , Trivieri Maria Giovanna , Contreras Johanna P. , Burkhoff Daniel , Moss Noah , Mancini Donna M. , Pinney Sean P.
Published: December 2020

Aims

Readmission after hospitalization for acute decompensated heart failure (HF) remains a major public health problem. Use of remote dielectric sensing (ReDS) to measure lung water volume allows for an objective assessment of volume status and may guide medical optimization for HF. We hypothesized that the use of ReDS would lower 30 day readmission in patients referred to rapid follow‐up (RFU) clinic after HF discharge.

Methods and results

We conducted a retrospective analysis of the use of ReDS for patients scheduled for RFU within 10 days post‐discharge for HF at Mount Sinai Hospital between 1 July 2017 and 31 July 2018. Diuretics were adjusted using a pre‐specified algorithm. The association between use of ReDS and 30 day readmission was evaluated. A total of 220 patients were included. Mean age was 62.9 ± 14.7 years, and 36.4% were female. ReDS was performed in 80 (36.4%) and led to medication adjustment in 52 (65%). Use of ReDS was associated with a lower rate of 30 day cardiovascular readmission [2.6% vs. 11.8%, hazard ratio (HR): 0.21; 95% confidence interval (CI): 0.05–0.89; P = 0.04] and a trend towards lower all‐cause readmission (6.5% vs. 14.1%, HR: 0.43; 95% CI: 0.16–1.15; P = 0.09) as compared with patients without a ReDS assessment.

Conclusions

ReDS‐guided HF therapy during RFU after HF hospitalization may be associated with lower risk of 30 day readmission.
An Overview of Flexible Electrode Materials/Substrates for Flexible Electrochemical Energy Storage/Conversion Devices
Authors: Shang Kezheng , Gao Jiyuan , Yin Ximeng , Ding Yichun , Wen Zhenhai
Published: December 2020

The rise of portable and wearable electronics has largely stimulated the development of flexible energy storage and conversion devices. As one of the essential parts, the electrode plays critical role in determining the device performance, which required to be highly flexible, light‐weight, and conformable for flexible and wearable applications. However, it remains a formidable challenge in the design of appropriate flexible electrodes. Thus, considerable effort has been making to develop various flexible materials/substrates to fabricate flexible energy devices. Here, this review aims to provide a comprehensive survey on the recently developed free‐standing and flexible electrode materials/substrates for flexible electrochemical energy storage devices, which are categorized into four different types including metal‐based, carbon‐based, polymer‐based, and micro‐patterned flexible electrodes. The specific characteristics, fabrication methods, properties, and pros and cons of each type of materials are thoroughly analysed. Furthermore, challenges and future directions for designing flexible electrode materials are also discussed.
On the Regioselectivity of the Gould–Jacobs Reaction: Gas‐Phase Versus Solution‐Phase Thermolysis
Authors: Wernik Michaela , Hartmann Peter E. , Sipos Gellért , Darvas Ferenc , Boese A. Daniel , Dallinger Doris , Kappe C. Oliver
Published: December 2020

A detailed investigation of the regioselectivity in the thermal cyclization of (pyridyl)aminomethylenemalonates both in the gas‐ and solution phase is presented. Flash vacuum pyrolysis (FVP) as a gas‐phase thermolysis technique is used to study the Gould–Jacobs reaction at temperatures between 450–650 °C, while different solution‐phase heating techniques (reflux, microwave, and continuous flow) were employed at 260–350 °C. Depending on the position of the substituent in the pyridine moiety and the applied thermolysis technique, the regioselectivity of the cyclization can be controlled either in favor of the kinetic (pyridopyrimidinone) or the thermodynamic (naphthyridinone) product. Under FVP conditions, 6‐substituted pyridopyrimidinones were obtained in high regioselectivity, which was not demonstrated before under standard Gould–Jacobs reaction conditions. DFT calculations have been additionally performed to provide further insights into the mechanistic pathways of this specific Gould–Jacobs reaction.
Studies towards Pyridine‐Based N,N,O‐Gold(III) Complexes: Synthesis, Characterization and Application
Authors: Solvi Thomas Nordbø , Reiersølmoen Ann Christin , Orthaber Andreas , Fiksdahl Anne
Published: December 2020

Gold(III) coordination of new chiral polydentate (N,)N,O‐pyridine based ligands is reported. Successful coordination afforded novel chiral N,N,O‐tridentate Au(III) complexes with the 2‐pyridyl‐6‐[(1S,2S,5R)‐neomenthol‐1‐yl]pyridine ligand (1H, 13C, 15N NMR, HRMS, IR, XRD). The chiral 2‐aryl‐6‐alkylpyridine alcohol ligands were prepared from 2,6‐dibromopyridine by initial stereoselective addition to (–)‐menthone and (+)‐camphor, respectively, and subsequent Suzuki cross‐coupling with a series arylboronic acids. Testing of catalytic activity in propargyl cyclopropanation demonstrated that the new N,N,O‐ligated gold(III) complex was highly catalytic active and outperformed AuCl3.
Cu‐Mediated Radiofluorination of Aryl Pinacolboronate Esters: Alcohols as Solvents with Application to 6‐L‐[18F]FDOPA Synthesis
Authors: Orlovskaya Viktoriya , Fedorova Olga , Kuznetsova Olga , Krasikova Raisa
Published: December 2020

Cu‐mediated radiofluorination of arylboronic acid pinacol esters (ArylBPin) using Cu(OTf)2(Py)4 complex is a useful approach for the introduction of [18F]fluorine into non‐activated arenes and heteroarenes. Owing to the complexity of the mechanism and wide variation in substrate reactivity the choice of reaction conditions must be made individually for every precursor. Careful selection of phase‐transfer catalysts also plays a role, as Cu‐catalyst and ArylBPin precursors are known to be unstable in basic conditions. Using tetrabutylammonium triflate alcohol solution for elution of [18F]fluoride from ion‐exchange cartridge and employing same alcohol as a co‐solvent in the following labelling step, we have developed a general protocol resulting in >80 % fluorination efficiency of ArylBPin precursors for 4‐[18F]fluoro‐D,L‐phenylalanine and 6‐L‐[18F]FDOPA. Radiofluorination in neat alcohol was particularly effective for the synthesis of 6‐L‐[18F]FDOPA, allowing for substantial increase of yield and decrease of synthesis time compared to current methods (activity yield 14.5 ± 0.5 %, 70 min synthesis time).
Double Porphyrin Cage Compounds
Authors: Stout Kathleen , Peters Theo P. J. , Mabesoone Mathijs F. J. , Visschers Fabian L. L. , Meijer Eline M. , Klop Joëlle‐Rose , van den Berg Jeroen , White Paul B. , Rowan Alan E. , Nolte Roeland J. M. , Elemans Johannes A. A. W.
Published: December 2020

The synthesis and characterization of double porphyrin cage compounds are described. They consist of two porphyrins that are each attached to a diphenylglycoluril‐based clip molecule via four ethyleneoxy spacers, and are linked together by a single alkyl chain using “click”‐chemistry. Following a newly developed multistep synthesis procedure we report three of these double porphyrin cages, linked by spacers of different lengths, i.e. 3, 5, and 11 carbon atoms. The structures of the double porphyrin cages were fully characterized by NMR, which revealed that they consist of mixtures of two diastereoisomers. Their zinc derivatives are capable of forming sandwich‐like complexes with the ditopic ligand 1,4‐diazabicyclo[2,2,2]octane (dabco).