bluuebunny/crossref_metadata_2025 huggingface dataset:
Self‐Adjuvanted Molecular Activator (SeaMac) Nanovaccines Promote Cancer Immunotherapy
Authors: Luo Zichao , He Tao , Liu Peng , Yi Zhigao , Zhu Shunyao , Liang Xiuqi , Kang Entang , Gong Changyang , Liu Xiaogang
Published: December 2020

Neoantigen‐based immunotherapy is a promising treatment option for many types of cancer. However, its efficacy and abscopal effect are limited by impotent neoantigens, high treatment costs, and complications due to action of adjuvants. Here, the design and synthesis of nanovaccines are reported, based on self‐adjuvanted, polymer nanoparticles with in vivo neoantigen‐harvesting and molecular activating capabilities. These nanovaccines inhibit tumor growth significantly and prolong the survival of tumor‐bearing mice in both colon carcinoma 26 (CT26) and B16‐F10 tumor models. Mechanistic studies suggest that as‐synthesized nanovaccines can promote dendritic cell maturation and accumulation expeditiously in lymph nodes, leading to the expansion of cytotoxic CD8+ T cells. Moreover, these nanovaccines elicit abscopal effects in CT26 and B16‐F10 tumors without the need for adjuvants or immune checkpoint inhibitors. Combined with an anti‐PD‐L1 antibody, nanovaccines can evoke robust, long‐term memory immune response, as evidenced by tumor growth inhibition and high survival rates (∼ 67%) over 90 days. These results highlight the potential of using self‐adjuvanted nanovaccines as a simple, safe, and affordable strategy to boost neoantigen‐based cancer immunotherapy.
Locomotion of Miniature Soft Robots
Authors: Ng Chelsea Shan Xian , Tan Matthew Wei Ming , Xu Changyu , Yang Zilin , Lee Pooi See , Lum Guo Zhan
Published: December 2020

Miniature soft robots are mobile devices, which are made of smart materials that can be actuated by external stimuli to realize their desired functionalities. Here, the key advancements and challenges of the locomotion producible by miniature soft robots in micro‐ to centimeter length scales are highlighted. It is highly desirable to endow these small machines with dexterous locomotive gaits as it enables them to easily access highly confined and enclosed spaces via a noninvasive manner. If miniature soft robots are able to capitalize this unique ability, they will have the potential to transform a vast range of applications, including but not limited to, minimally invasive medical treatments, lab‐on‐chip applications, and search‐and‐rescue missions. The gaits of miniature soft robots are categorized into terrestrial, aquatic, and aerial locomotion. Except for the centimeter‐scale robots that can perform aerial locomotion, the discussions in this report are centered around soft robots that are in the micro‐ to millimeter length scales. Under each category of locomotion, prospective methods and strategies that can improve their gait performances are also discussed. This report provides critical analyses and discussions that can inspire future strategies to make miniature soft robots significantly more agile.
Soft Ferroelectrics Enabling High‐Performance Intelligent Photo Electronics
Authors: Park Chanho , Lee Kyuho , Koo Min , Park Cheolmin
Published: December 2020

Soft ferroelectrics based on organic and organic–inorganic hybrid materials have gained much interest among researchers owing to their electrically programmable and remnant polarization. This allows for the development of numerous flexible, foldable, and stretchable nonvolatile memories, when combined with various crystal engineering approaches to optimize their performance. Soft ferroelectrics have been recently considered to have an important role in the emerging human‐connected electronics that involve diverse photoelectronic elements, particularly those requiring precise programmable electric fields, such as tactile sensors, synaptic devices, displays, photodetectors, and solar cells for facile human–machine interaction, human safety, and sustainability. This paper provides a comprehensive review of the recent developments in soft ferroelectric materials with an emphasis on their ferroelectric switching principles and their potential application in human‐connected intelligent electronics. Based on the origins of ferroelectric atomic and/or molecular switching, the soft ferroelectrics are categorized into seven subgroups. In this review, the efficiency of soft ferroelectrics with their distinct ferroelectric characteristics utilized in various human‐connected electronic devices with programmable electric field is demonstrated. This review inspires further research to utilize the remarkable functionality of soft electronics.
Twisted Biphenyl‐Diimide Derivatives with Aggregation‐Induced Emission and Thermally Activated Delayed Fluorescence for High Performance OLEDs
Authors: Wang Zhijun , Zhu Xiangyu , Zhang Sikun , Xu Letian , Zhao Zujin , He Gang
Published: December 2020

π‐Conjugated arylene diimide derivatives as a kind of well‐known organic dyes have been widely used as building blocks for constructing n‐type semiconductors. However, the large π‐framework faded their solid‐state emission, which hinders their application in organic light‐emitting diodes (OLEDs). Herein, two novel π‐conjugated donor–acceptor–donor (D‐A‐D) type compounds BPI‐PhPXZ and BPI‐PhDMAC, composed of twisted biphenyl‐diimide (BPI) acceptors and phenoxazine or acridine donors are synthesized. BPI‐PhPXZ and BPI‐PhDMAC show prominent aggregation‐induced emission (AIE) and thermally activated delayed fluorescence (TADF), and enjoy good thermal and electrochemical stabilities. Doped OLEDs fabricated with the two compounds have achieved high external quantum efficiencies (EQEs) of 18.1% and 16.2%, respectively. The results highlight the beneficial role of well‐designed BPI acceptor for the development of efficient D‐A‐D type TADF emitters with AIE properties.
Optical Chirality Enhancement in Hollow Silicon Disk by Dipolar Interference
Authors: Du Kang , Li Pei , Wang Heng , Gao Kun , Liu Rui‐Bin , Lu Fanfan , Zhang Wending , Mei Ting
Published: December 2020

Optical chirality enhancement is highly demanded for enantioselective interaction of circularly polarized light with chiral molecules. The chirality enhancement in the coaxial air hole of a hollow silicon disk depends on three aspects, namely, the enhancements of electric and magnetic fields and a factor determined by the phases of their field components. In the spectral regime of dipole resonances, maximum chirality enhancement with sign consistency and uniform spatial distribution in the air hole can be obtained in association with both magnetic dipole resonance and anapole. Due to dipolar interference, the chirality is nulled at their coincidence, around which the sign of chirality is reversed. Maximum chirality with both positive and negative signs can be found between magnetic dipole resonance and anapole in the vicinity of their coincidence. This situation is maintained under size scaling so that the operation wavelength can be broadly tuned. The optical chirality can be further improved by merely adjusting the hole radius, by which the optimal spatially averaged optical chirality enhancement factor can reach 39 and −23. The simple strategy for optimizing Mie resonators presented in this work may benefit the design of Mie resonator‐based achiral metasurfaces for chirality detection application.
Asymmetric Synthesis of Chiral Amino Carboxylic‐Phosphonic Acid Derivatives
Authors: Cao Hao‐Qiang , Li Jun‐Kuan , Zhang Fa‐Guang , Cahard Dominique , Ma Jun‐An
Published: December 2020

Chiral amino acids featuring a phosphonate pendant arm are an important type of biologically active scaffold. Here in this review, we comprehensively summarize the modern synthetic methods towards asymmetric construction of chiral amino carboxylic‐phosphonic acid derivatives. The main streams of such interesting compounds include phosphono‐containing α‐, β‐, and γ‐amino acid derivatives, amino acid fluorophosphonate derivatives, amino acid cyclopropanylphosphonate derivatives, and bisphosphono‐amino acid derivatives. Chiral resolution protocols, chiral auxiliary‐directed syntheses, and valorization of the pool of abundant chiral amino acid resources remain contemporary concerns, and meanwhile catalytic enantioselective synthesis has also emerged as a potent strategy as demonstrated by the latest advances.

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Confinement Aided Simultanous Water Cleaning and Energy Harvesting Using Atomically Thin Wurtzite (Wurtzene)
Authors: Kumbhakar Partha , Mukherjee Madhubanti , Pramanik Ashim , Karmakar Srikanta , Singh Abhishek K. , Tiwary Chandra S. , Kumbhakar Pathik
Published: December 2020

Syntheses of few‐layered piezocatalysts from nonlayered materials have gained a huge attention of attention in recent years due to their potential applicability in efficient removal of toxic elements from water. Here, a simple scalable bottom up approach consisting of wet‐chemical synthesis method is used to produce the atomically thin (2D)‐wurtzite ZnO: “wurtzene.” The presence of a large number of well‐distributed surface defects in the synthesized wurtzene promotes the separation of charge carriers in it via the excellent piezo‐photocatalytic activity and thereby the efficiency of degradation of a test dye (namely methylene blue) is enhanced by ≈5 times. By taking an innovative approach, a piezoelectric driven power cell is also fabricated by using the wurtzene and the highest open circuit voltage is found out to be ≈40 V at 1.0 kPa of applied periodic pressure. The experimental observations are explained with density functional theory calculation. The confinement effect due to reduced dimension plays a crucial role in the wurtzene's excellent piezoelectric response. It is envisioned that the present findings will provided a clear insight into the synthesis of wurtzene with surface defects for highly efficient sunlight driven photocatalytic activity as well as piezoelectric energy harvesting.
Insights into the Nanostructure, Solvation, and Dynamics of Liquid Electrolytes through Small‐Angle X‐Ray Scattering
Authors: Qian Kun , Winans Randall E. , Li Tao
Published: December 2020

The fundamental understanding of nanostructures of liquid electrolytes is expected to enable transformative gains in electrochemical energy storage capacities. However, the solvation structures and molecular dynamics in electrolytes are hard to probe, which limits further performance improvements in macroscopic properties such as ionic conductivity, viscosity, and stability. Small‐angle X‐ray scattering (SAXS), a non‐destructive method for nanostructures characterization in liquids, offers a unique perspective on molecular clusters, anion‐cation pairs, solvation sheath, percolating network, aggregates, and domain sizes of electrolytes. Notably, the SAXS method has excellent time‐resolution, enabling the study of molecular dynamics by operando characterization. This review focuses on the microscopic understanding of liquid electrolytes by SAXS and operando SAXS. The unique capabilities of X‐ray scattering for intra‐ and inter‐molecular relationship and nanostructure characterization of electrolytes are highlighted.
Electrocatalytic Oxygen Reduction to Hydrogen Peroxide: From Homogeneous to Heterogeneous Electrocatalysis
Authors: Wang Yulin , Waterhouse Geoffrey I. N. , Shang Lu , Zhang Tierui
Published: December 2020

Hydrogen peroxide (H2O2) is an environmentally friendly oxidant, finding widespread use across the chemical industry, in sanitation and environmental remediation. Currently, H2O2 is manufactured via the anthraquinone process which has a number of disadvantages including nondistributed production, high‐energy consumption, substantial organic by‐product waste, and the need to transport the obtained H2O2 to the point‐of‐use. Accordingly, the electrochemical synthesis of H2O2 is now attracting a lot of interest as an alternative, cost‐effective, small‐scale, and distributed technology for H2O2 manufacture. This review summarizes recent advancements in the development of Homogeneous and Heterogeneous catalysts for electrocatalytic O2 reduction reaction (ORR) to H2O2. The basic principles of the ORR, and methodologies for investigating the ORR to H2O2 are first introduced. Next, H2O2 production over Homogeneous catalysts is discussed, with a focus on the reaction mechanisms and the factors that influence activity, selectivity, and reaction kinetics. Subsequently, recent breakthroughs in H2O2 synthesis over Heterogeneous catalysts, including nonnoble metal‐based nanomaterials, carbon materials, and single‐atom catalysts are described. The latter are given special attention, since they serve as a bridge between Homogeneous catalysis and Heterogeneous catalysis, while also offering excellent performance. Finally, the challenges and opportunities for electrochemical ORR to H2O2 are critically discussed.
The screened waveguide for intrusive acoustic emission detection and its application in circulating fluidized bed
Authors: Sheng Tao , Zhang Peng , Huang Zhengliang , Yang Yao , Sun Jingyuan , Jiang Binbo , Ding Xingcheng , Wang Jingdai , Yang Yongrong , Liao Zuwei
Published: December 2020

A screened waveguide with a 90° elbow, which had a rubber surface to reduce noise generations and a steel/air interface to block noise propagations, was designed to measure local particle movements in certain directions. In the riser of circulating fluidized bed, the noise energy only accounted for 2.1% of the total energy received by the waveguide. Besides, the radial acoustic emission energy distribution detected via the waveguide was highly consistent with the radial solid flux distribution measured by the extraction probe. Furthermore, the radial flow patterns in the riser with Geldart D particles were measured under dense phase conveying by this new method, which always demonstrated as core‐annulus flows and the transition points (r/R) increased with decreasing solid–gas ratios.
Successful pregnancies in an adult with Meier‐Gorlin syndrome harboring biallelic CDT1 variants
Authors: Knapp Karen M. , Murray Jennie , Temple I. Karen , Bicknell Louise S.
Published: December 2020

Meier‐Gorlin syndrome is an autosomal recessively inherited disorder of growth retardation, accompanied by microtia and patellae a/hypoplasia and characteristic facies. Pathogenic variants in genes associated with the initiation of DNA replication underlie the condition, with biallelic variants in CDT1 the most common cause. Using 10× Chromium genome sequencing, we report CDT1 variants in an adult female, with an inframe amino acid deletion inherited in trans with a deep intronic variant which likely serves as the branchpoint site in Intron 8. Splicing defects arising from this variant were confirmed through in vitro analysis. At 49 years, she represents the oldest patient with a molecular diagnosis described in the literature and is the first reported patient with Meier‐Gorlin syndrome to have carried a successful pregnancy to term. Both of her pregnancies were complicated by postpartum hemorrhage and upon subsequent necessary hysterectomy, revealed uterine abnormalities. There is scant knowledge on reproductive ability and success in patients with Meier‐Gorlin syndrome. Successful pregnancies among other clinically recognizable forms of primordial dwarfism have also not been described previously. This case is therefore of clinical interest for many forms of inherited growth retardation, and will assist in providing more information and clinical guidance for females of reproductive age.
An examination of a novel multipanel of CSF biomarkers in the Alzheimer's disease clinical and pathological continuum
Authors: Van Hulle Carol , Jonaitis Erin M. , Betthauser Tobey J. , Batrla Richard , Wild Norbert , Kollmorgen Gwendlyn , Andreasson Ulf , Okonkwo Ozioma , Bendlin Barbara B. , Asthana Sanjay , Carlsson Cynthia M. , Johnson Sterling C. , Zetterberg Henrik , Blennow Kaj
Published: December 2020

Introduction

This study examines the utility of a multipanel of cerebrospinal fluid (CSF) biomarkers complementing Alzheimer's disease (AD) biomarkers in a clinical research sample. We compared biomarkers across groups defined by clinical diagnosis and pTau181/Aβ42 status (+/−) and explored their value in predicting cognition.

Methods

CSF biomarkers amyloid beta (Aβ)42, pTau181, tTau, Aβ40, neurogranin, neurofilament light (NfL), α‐synuclein, glial fibrillary acidic protein (GFAP), chitinase‐3‐like protein 1 (YKL‐40), soluble triggering receptor expressed on myeloid cells 2 (sTREM2), S100 calcium binding protein B (S100B), and interleukin 6 (IL6), were measured with the NeuroToolKit (NTK) for 720 adults ages 40 to 93 years (mean age = 63.9 years, standard deviation [SD] = 9.0; 50 with dementia; 54 with mild cognitive impairment [MCI], 616 unimpaired).

Results

Neurodegeneration and glial activation biomarkers were elevated in pTau181/Aβ42+ MCI/dementia participants relative to all pTau181/Aβ42‐ participants. Neurodegeneration biomarkers increased with clinical severity among pTau181/Aβ42+ participants and predicted worse cognitive performance. Glial activation biomarkers were unrelated to cognitive performance.

Discussion

The NTK contains promising markers that improve the pathophysiological characterization of AD. Neurodegeneration biomarkers beyond tTau improved statistical prediction of cognition and disease stages.
Room‐Temperature Palladium‐Catalyzed Deuterogenolysis of Carbon Oxygen Bonds towards Deuterated Pharmaceuticals
Authors: Ou Wei , Xiang Xudong , Zou Ru , Xu Qing , Loh Kian Ping , Su Chenliang
Published: December 2020

Site‐specific incorporation of deuterium into drug molecules to study and improve their biological properties is crucial for drug discovery and development. Herein, we describe a palladium‐catalyzed room‐temperature deuterogenolysis of carbon–oxygen bonds in alcohols and ketones with D2 balloon for practical synthesis of deuterated pharmaceuticals and chemicals with benzyl‐site (sp3 C−H) D‐incorporation. The highlights of this deoxygenative deuteration strategy are mild conditions, broad scope, practicability and high chemoselectivity. To enable the direct use of D2O, electrocatalytic D2O‐splitting is adapted to in situ supply D2 on demand. With this system, the precise incorporation of deuterium in the metabolic position (benzyl‐site) of ibuprofen is demonstrated in a sustainable and practical way with D2O.
[Mo3S13]2− als Modellsystem für die katalytische Wasserstoffentwicklung durch MoSx: Untersuchung der Protonierungsstellen in der Gasphase durch Infrarot‐Mehrphotonendissoziationsspektroskopie
Authors: Baloglou Aristeidis , Plattner Manuel , Ončák Milan , Grutza Marie‐Luise , Kurz Philipp , Beyer Martin K.
Published: December 2020

Materialien auf Molybdänsulfidbasis sind als effiziente Katalysatoren für die Wasserstoffentwicklung (hydrogen evolution reaction, HER) bekannt. Da die Bindungsstelle des H‐Atoms an MoSx in der Diskussion steht, stellt [HMo3S13]− ein interessantes molekulares Modellsystem dar, um dieser Frage auf den Grund zu gehen. Hier wird der Cluster [HMo3S13]− in der Gasphase mittels Fourier‐Transformations‐Ionenzyklotronresonanz‐Massenspektrometrie (FT‐ICR MS), gekoppelt mit Infrarot‐Mehrphotonendissoziationsspektroskopie (IRMPD), untersucht. Unsere Untersuchungen zeigen eine deutliche S‐H‐Streckschwingung bei 2450 cm−1. Thermochemische Argumente auf der Grundlage von DFT‐Rechnungen deuten stark darauf hin, dass die beobachtete H‐Adsorption an einer terminalen Disulfideinheit stattfindet.
Concentration‐Dependent Subcellular Distribution of Ultrasmall Near‐Infrared‐Emitting Gold Nanoparticles
Authors: Gong Lingshan , He Kui , Liu Jinbin
Published: December 2020

The ability to accurately control the subcellular distribution of nanomedicines provides unique advantages on understanding of cellular biology and disease theranostics. The nanomedicine concentration is a key factor to affect the theranostic efficiency and systematic toxicity. Herein, we unravel a concentration‐dependent subcellular distribution of near‐infrared‐emitting gold nanoparticles (AuNPs) co‐coated with glutathione and a cell‐penetrating peptide CR8 (CR‐AuNPs), which shows a strong membrane‐binding at high concentration but more endocytosis for mitochondria targeting at the low concentration region. Attributing to high content of AuI and microsecond luminescent lifetimes, these AuNPs can catalyze dissolved oxygen to generate singlet oxygen (1O2) efficiently. Combining with the concentration‐dependent subcellular distribution, the luminescent AuNPs show photocytotoxicity in the relative low concentration region. These findings facilitate the fundamental understanding of the biological behaviors and potential cytotoxicity of ultrasmall luminescent AuNPs toward future theranostics.
Selective Chemical Upcycling of Mixed Plastics Guided by a Thermally Stable Organocatalyst
Authors: Jehanno Coralie , Demarteau Jeremy , Mantione Daniele , Arno Maria C. , Ruipérez Fernando , Hedrick James L. , Dove Andrew P. , Sardon Haritz
Published: December 2020

Chemical recycling of plastic waste represents a greener alternative to landfill and incineration, and potentially offers a solution to the environmental consequences of increased plastic waste. Most plastics that are widely used today are designed for durability, hence currently available depolymerisation methods typically require harsh conditions and when applied to blended and mixed plastic feeds generate a mixture of products. Herein, we demonstrate that the energetic differences for the glycolysis of BPA‐PC and PET in the presence of a protic ionic salt TBD:MSA catalyst enables the selective and sequential depolymerisation of these two commonly employed polymers. Employing the same procedure, functionalised cyclic carbonates can be obtained from both mixed plastic wastes and industrial polymer blend. This methodology demonstrates that the concept of catalytic depolymerisation offers great potential for selective polymer recycling and also presents plastic waste as a “greener” alternative feedstock for the synthesis of high added value molecules.
Biocatalytic Strategy for the Highly Stereoselective Synthesis of CHF2‐Containing Trisubstituted Cyclopropanes
Authors: Carminati Daniela M. , Decaens Jonathan , Couve‐Bonnaire Samuel , Jubault Philippe , Fasan Rudi
Published: December 2020

The difluoromethyl (CHF2) group has attracted significant attention in drug discovery and development efforts, owing to its ability to serve as fluorinated bioisostere of methyl, hydroxyl, and thiol groups. Herein, we report an efficient biocatalytic method for the highly diastereo‐ and enantioselective synthesis of CHF2‐containing trisubstituted cyclopropanes. Using engineered myoglobin catalysts, a broad range of α‐difluoromethyl alkenes are cyclopropanated in the presence of ethyl diazoacetate to give CHF2‐containing cyclopropanes in high yield (up to >99 %, up to 3000 TON) and with excellent stereoselectivity (up to >99 % de and ee). Enantiodivergent selectivity and extension of the method to the stereoselective cyclopropanation of mono‐ and trifluoromethylated olefins was also achieved. This methodology represents a powerful strategy for the stereoselective synthesis of high‐value fluorinated building blocks for medicinal chemistry, as exemplified by the formal total synthesis of a CHF2 isostere of a TRPV1 inhibitor.
Rhodium‐Catalyzed Atroposelective Construction of Indoles via C−H Bond Activation
Authors: Sun Lincong , Chen Haohua , Liu Bingxian , Chang Junbiao , Kong Lingheng , Wang Fen , Lan Yu , Li Xingwei
Published: December 2020

Reported herein is the rhodium(III)‐catalyzed C−H activation of anilines bearing an N‐isoquinolyl directing group for oxidative [3+2] annulation with four classes of internal alkynes, leading to atroposelective indole synthesis via dynamic kinetic annulation with C‐N reductive elimination constituting the stereo‐determining step. This reaction proceeds under mild conditions with high regio‐ and enantioselectivity and functional group compatibility.
[Mo3S13]2− as a Model System for Hydrogen Evolution Catalysis by MoSx: Probing Protonation Sites in the Gas Phase by Infrared Multiple Photon Dissociation Spectroscopy
Authors: Baloglou Aristeidis , Plattner Manuel , Ončák Milan , Grutza Marie‐Luise , Kurz Philipp , Beyer Martin K.
Published: December 2020

Materials based on molybdenum sulfide are known as efficient hydrogen evolution reaction (HER) catalysts. As the binding site for H atoms on molybdenum sulfides for the catalytic process is under debate, [HMo3S13]− is an interesting molecular model system to address this question. Herein, we probe the [HMo3S13]− cluster in the gas phase by coupling Fourier‐transform ion‐cyclotron‐resonance mass spectrometry (FT‐ICR MS) with infrared multiple photon dissociation (IRMPD) spectroscopy. Our investigations show one distinct S−H stretching vibration at 2450 cm−1. Thermochemical arguments based on DFT calculations strongly suggest a terminal disulfide unit as the H adsorption site.
Zirconia‐dispersedpolyethylene glycol composites with a lowtemperature‐degradationrate
Authors: Hilmi Allif Rosyidy , Muwwaqor Nibras Fuadi , Fauziyah Nur Aini , Pratapa Suminar
Published: December 2020

The effect of tetragonal‐zirconia nanoparticle inclusion on the temperature‐dependent storage modulus, or the temperature‐degradation rate, of polyethylene glycol (PEG)‐based composites was investigated using shear‐mode dynamic mechanical analysis (DMA) at temperatures ranging from room temperature up to 75°C. We carried out further investigations in the rubbery area in terms of the characteristic of the degradation rate with temperature and compared it with silica‐quartz‐filled PEG composites, which exhibited a potential as phase‐change materials (PCMs). The investigation began by plotting the shear storage modulus (G′) of the composites and observing the slopes of the curves in the range of the rubbery area, which were assumed to follow a straight‐line equation. Then, we completed the investigation by developing and introducing a temperature‐dependent storage modulus model in the rubbery area for describing the storage modulus of such filler‐dispersed PEG/inorganic composites, to yield the degradation rates of the composites. The new model includes parametersk1andCthat are associated with the degradation rate and the amount of a filler, respectively. The model shows a satisfactory agreement with the experimental data ofG′in the rubbery area, being parameterk1is associated with a linear degradation rate.
Hydrophobic stretchable polydimethylsiloxane films with wrinkle patterns prepared via a metal‐assisted chemical etching process using a Si master mold
Authors: Lee Hanbin , Chae Sangmin , Yi Ahra , Kim Hyo Jung
Published: December 2020

We fabricated hydrophobic, stretchable, wrinkle‐patterned polydimethylsiloxane (PDMS) films via a metal‐assisted chemical etching (MACE) process using a Si master mold, which is a mask‐free technique for fabricating large‐area films. The wrinkle‐patterned PDMS surface prepared via MACE exhibited high hydrophobicity and stretchability, which are difficult to achieve with wrinkle‐patterned PDMS prepared via a conventional process, such as, plasma treatment, e‐beam, or laser patterning. The contact angle of the wrinkled PDMS surface was dependent on the size of the micro/nanostructures, and the largest contact angle was 135.8 ± 0.1° for the film prepared under the optimum conditions. To confirm the applicability of the wrinkled PDMS films to flexible electronics, we tuned the mechanical properties by controlling the crosslinker ratio in the films. The Young's modulus ranged from 0.193 to 1.364 MPa depending on the crosslinker ratio, and the stress of the optimum film was 1.5 MPa under 250% strain.
Well‐Dispersed Trifluoromethanesulfonic Acid‐Treated Metal Oxide Nanoparticles Immobilized on Nitrogen‐Doped Carbon as Catalysts for Friedel–Crafts Acylation
Authors: Yang Xi , Yasukawa Tomohiro , Maki Tei , Yamashita Yasuhiro , Kobayashi Shū
Published: December 2020

Although strong acid‐treated metal oxides are useful heterogeneous superacid catalysts for various organic transformations, they usually have a limited density of acidic sites due to their low surface areas. Herein, heterogeneous trifluoromethanesulfonic acid immobilized nitrogen‐doped carbon‐incarcerated titanium nanoparticle (NP) catalysts have been developed that are composed of well‐dispersed, small Ti NPs (ca 7 nm) that are otherwise difficult to achieve using acid‐treated metal oxides. The catalysts showed high activity for Friedel–Crafts acylation with low titanium loading (2 mol%, <1 mg of metal for 1 mmol of substrate). A range of microscopic, spectroscopic and physicochemical studies revealed that the nitrogen‐doped carbon immobilized the trifluoromethanesulfonic acid and that the addition of metals further changed the nature of the acidic species and enhanced catalytic activity.
Micelle‐enhanced spectrofluorimetric determination of diphenhydramine: application to human plasma and its simultaneous determination with naproxen in pharmaceutical tablets
Authors: Hammad Sherin F. , El‐Khateeb Basma Z. , El‐Malla Samah F.
Published: December 2020

Two simple and sensitive spectrofluorimetric methods were developed and validated for determination of diphenhydramine. The use of sodium dodecyl sulfate surfactant at pH 7 enhances the fluorescence intensity of diphenhydramine at 286 nm (method I) enabling its nanodetermination in biological samples with mean per cent recovery ± SD of 100.33 ± 1.519. Method I was validated according to ICH‐Q2R1 guidelines and was successfully applied for determination of diphenhydramine in pharmaceutical dosage form and spiked human plasma in the concentration ranges 0.1–4.0 μg/mL and 0.2–1.0 μg/mL, respectively. Method I acted as a basis for the development of a first derivative synchronous spectrofluorimetry (method II) for simultaneous analysis of diphenhydramine and naproxen using a zero‐crossing approach. Method II determines both drugs with linearity ranges of 0.05–3.0 μg/mL and 0.1–0.9 μg/mL for diphenhydramine and naproxen, respectively. The developed method was applied for the simultaneous determination of both drugs in their laboratory‐prepared mixtures containing all expected excipients. Method II determines both drugs with a mean percent recovery ± SD of 100.56 ± 0.891 and 100.20 ± 1.125 for diphenhydramine and naproxen, respectively. The method was statistically compared with a reported method using Student's t‐ and F‐ tests, and no significant differences were observed.
Introduction of glycine synthase enables uptake of exogenous formate and strongly impacts the metabolism in Clostridium pasteurianum
Authors: Hong Yaeseong , Arbter Philipp , Wang Wei , Rojas Lilian N. , Zeng An‐Ping
Published: December 2020

Autotrophic or mixotrophic use of one‐carbon (C1) compounds is gaining importance for sustainable bioproduction. In an effort to integrate the reductive glycine pathway (rGP) as a highly promising pathway for the assimilation of CO2 and formate, genes coding for glycine synthase system from Gottschalkia acidurici were successfully introduced into Clostridium pasteurianum, a non‐model host microorganism with industrial interests. The mutant harboring glycine synthase exhibited assimilation of exogenous formate and reduced CO2 formation. Further metabolic data clearly showed large impacts of expression of glycine synthase on the product metabolism of C. pasteurianum. In particular, 2‐oxobutyrate (2‐OB) was observed for the first time as a metabolic intermediate of C. pasteurianum and its secretion was solely triggered by the expression of glycine synthase. The perturbation of C1 metabolism is discussed regarding its interactions with pathways of the central metabolism, acidogenesis, solventogenesis, and amino acid metabolism. The secretion of 2‐OB is considered as a consequence of metabolic and redox instabilities due to the activity of glycine synthase and may represent a common metabolic response of Clostridia in enhanced use of C1 compounds.
Parcellation‐based anatomic modeling of the default mode network
Authors: Sandhu Zainab , Tanglay Onur , Young Isabella M. , Briggs Robert G. , Bai Michael Y. , Larsen Micah L. , Conner Andrew K. , Dhanaraj Vukshitha , Lin Yueh‐Hsin , Hormovas Jorge , Fonseka Rannulu Dineth , Glenn Chad A. , Sughrue Michael E.
Published: December 2020

Background

The default mode network (DMN) is an important mediator of passive states of mind. Multiple cortical areas, such as the anterior cingulate cortex, posterior cingulate cortex, and lateral parietal lobe, have been linked in this processing, though knowledge of network connectivity had limited tractographic specificity.

Methods

Using resting‐state fMRI studies related to the DMN, we generated an activation likelihood estimation (ALE). We built a tractographical model of this network based on the cortical parcellation scheme previously published under the Human Connectome Project. DSI‐based fiber tractography was performed to determine the structural connections between cortical parcellations comprising the network.

Results

Seventeen cortical regions were found to be part of the DMN: 10r, 31a, 31pd, 31pv, a24, d23ab, IP1, p32, POS1, POS2, RSC, PFm, PGi, PGs, s32, TPOJ3, and v23ab. These regions showed consistent interconnections between adjacent parcellations, and the cingulum was found to connect the anterior and posterior cingulate clusters within the network.

Conclusions

We present a preliminary anatomic model of the default mode network. Further studies may refine this model with the ultimate goal of clinical application.
Juggle the many roles of campus public safety during COVID‐19
Authors: Miles David
Published: December 2020

It usually takes me some time to come up with a topic for this column and then put my thoughts into words.
Labor laws, free speech rights at play in student‐athlete activism
Authors: McCarthy Claudine
Published: December 2020

T   he increased wave of student activism has forced colleges and universities to tackle a variety of social, legal, and communication challenges. Student‐athletes have played significant roles in marches and demonstrations; boycotts of practices and donor events; and demands to rename buildings, ban fight songs, remove campus monuments, and discipline coaching staff, noted Michael R. Phillips, Partner at McGuireWoods LLP.
Consider legal, compliance implications of partnering with sports‐betting organizations
Authors: O'Brien Timothy
Published: December 2020

Against the backdrop of the crushing impact of the pandemic on the budgets of athletics departments nationwide and across all divisions, institutions have begun to reimagine their approaches to revenue generation.
Association between mid‐term worsening renal function and mortality after transcatheter aortic valve replacement in patients with chronic kidney disease
Authors: Phan Derek Q. , Lee Ming‐Sum , Aharonian Vicken , Mansukhani Prakash , Moore Naing , Brar Somjot S. , Zadegan Ray
Published: December 2020

Introduction

Chronic kidney disease (CKD), acute kidney injury (AKI) and worsening renal function at 30 days after transcatheter aortic valve replacement (TAVR) portend poor outcomes. We sought to evaluate the association between worsening renal function at 3–6 months and mortality among patients with baseline renal dysfunction undergoing TAVR.

Methods

This is a retrospective study of patients with glomerular filtration rate (GFR) < 60 ml/min undergoing TAVR between June 2011 and March 2019 at the Regional Cardiac Catheterization Lab at Kaiser Permanente Los Angeles. Worsening renal function at 3–6 months post‐TAVR was defined as: increase in serum creatinine >1.5 times compared to baseline, absolute increase of ≥0.3 mg/dl, or initiation of dialysis.

Results

Of 683 patients reviewed, 176 were included in the analysis (median age 84 [IQR 79–88] years, 56% female). Of these, 27 (15.3%) had worsening renal function. AKI post‐TAVR (OR 2.9, 95% CI 1.1–7.4, p = .03) and transfusion of ≥4 units red blood cells (OR 8.4, 95% CI 1.2–59, p = .03) were independent predictors of worsening renal function. Worsening renal function increased risk for mortality (HR 2.2, 95% CI 1.17–4.27, p = .015) at a median follow‐up of 691 days. Those with improved/stable function with baseline GFR < 60 ml/min had comparable mortality risk to those with baseline GFR ≥ 60 ml/min (18% vs. 16.5%; HR 1.1, 95% CI 0.72–1.75, p = .62).

Conclusion

Among patients with baseline renal dysfunction, only 15% developed worsening renal function at 3–6 months after TAVR, which was associated with increased mortality. Predictors for worsening renal function include AKI and blood transfusions. Preventative measures peri‐procedurally and continued monitoring post‐discharge are warranted to improve outcomes.
Frontal lifting using a tissue expander in pachydermoperiostosis: A case report
Authors: Cunha Daniel José Dias , Pereira Rui Manoel Rodrigues , Leal Dantas Vasconcelos Nassar Julia , Xavier de Oliveira Junior Edilson , Ramos Jorge Luis Matta
Published: December 2020

Pachydermoperiostosis, a rare condition, is characterized by pachydermia, finger clubbing, and periostosis. We present an unusual treatment for frontal rhytids, for which we used a tissue expander that contributed to thinning of the skin and the depth of the rhytids prior to frontal lifting. The results were maintained after one year.
Toxic epidermal necrolysis associated with nivolumab treatment for head and neck cancer
Authors: Koshizuka Keiichi , Sakurai Daiju , Sunagane Miki , Mita Yukiyoshi , Hamasaki Sawako , Suzuki Takeshi , Kikkawa Naoko , Nakano Michiyo , Hanazawa Toyoyuki
Published: December 2020

This report is the first to document TEN caused by nivolumab treatment in head and neck cancer. We believe this article can contribute significantly in understanding the principles of nivolumab treatment in patients with head and neck cancer.
Establishment of dormant ‘Latitude 36’ bermudagrass sprigs in the transition zone
Authors: Herrmann Matthew , Goatley, James M. , McCall David S. , Askew Shawn D.
Published: December 2020

Improved vegetative bermudagrasses such as ‘Latitude 36’ [Cynodon dactylon (L.) Pers. × C. transvaalensis Burtt‐Davy] provide desirable playing surfaces for sports fields and golf courses in the transition zone of the United States because of their cold tolerance and exceptional density. However, establishing bermudagrass from vegetative stems (sprigs) during the standard planting times of mid‐spring through to mid‐summer in this region requires regular and frequent moisture after planting, essentially prohibiting the establishment of these grasses where supplemental irrigation is unavailable. Trials were conducted in 2017–2018 at the Turfgrass Research Center of Virginia Tech to evaluate the establishment success of sprigged Latitude 36 in January, February, or March under non‐irrigated conditions. Within sprig blocks, the addition of 0.25 inch compost, a turf blanket, and a combination of these were compared for improved establishment success. Digital image analysis was used to quantify green bermudagrass coverage over time. Ultimately, a targeted mean 90% bermudagrass coverage was achieved within 5 wk of removing the turf blankets in Blacksburg, VA, regardless of the initial sprigging date. Turf blankets alone and in combination with compost increased initial bermudagrass coverage after blanket removal but did not impact the final establishment rate. Data from these studies imply that hybrid bermudagrass can be sprigged successfully without irrigation during winter months, and that covering sprigs after planting had no long‐term impact on establishment.
Synthesis of Carbapenems Containing Peptidoglycan Mimetics and Inhibition of the Cross‐Linking Activity of a Transpeptidase of l,d Specificity
Authors: Saidjalolov Saidbakhrom , Edoo Zainab , Fonvielle Matthieu , Mayer Louis , Iannazzo Laura , Arthur Michel , Etheve‐Quelquejeu Mélanie , Braud Emmanuelle
Published: December 2020

The carbapenem class of β‐lactams has been optimized against Gram‐negative bacteria producing extended‐spectrum β‐lactamases by introducing substituents at position C2. Carbapenems are currently investigated for the treatment of tuberculosis as these drugs are potent covalent inhibitors of l,d‐transpeptidases involved in mycobacterial cell wall assembly. The optimization of carbapenems for inactivation of these unusual targets is sought herein by exploiting the nucleophilicity of the C8 hydroxyl group to introduce chemical diversity. As β‐lactams are structure analogs of peptidoglycan precursors, the substituents were chosen to increase similarity between the drug and the substrate. Fourteen peptido‐carbapenems were efficiently synthesized. They were more effective than the reference drug, meropenem, owing to the positive impact of a phenethylthio substituent introduced at position C2 but the peptidomimetics added at position C8 did not further improve the activity. Thus, position C8 can be modified to modulate the pharmacokinetic properties of highly efficient carbapenems.
Tetryl‐Tetrylene Addition to Phenylacetylene
Authors: Maudrich Jakob‐Jonathan , Diab Fatima , Weiß Sebastian , Zweigart Magda , Eichele Klaus , Schubert Hartmut , Müller Robert , Kaupp Martin , Wesemann Lars
Published: December 2020

Phenylacetylene adds [Ar*GeH2‐SnAr’], [Ar*GeH2‐PbAr’] and [Ar'SnH2‐PbAr*] at rt in a regioselective and stereoselective reaction. The highest reactivity was found for the stannylene, which reacts immediately upon addition of one equivalent of alkyne. However, the plumbylenes exhibit addition to the alkyne only in reaction with an excess of phenylacetylene. The product of the germylplumbylene addition reacts with a second equivalent of alkyne and the product of a CH‐activation, a dimeric lead acetylide, were isolated. In the case of the stannylplumbylene the trans‐addition product was characterized as the kinetically controlled product which isomerizes at rt to yield the cis‐addition product, which is stabilized by an intramolecular Sn–H–Pb interaction. NMR chemical shifts of the olefins were investigated using two‐ and four‐component relativistic DFT calculations, as spin–orbit effects can be large. Hydride abstraction was carried out by treating [Ar'SnPhC=CHGeH2Ar*] with the trityl salt [Ph3C][Al(OC{CF3})4] to yield a four membered ring cation.
Cyclo‐Ketal Xanthene Dyes: A New Class of Near‐Infrared Fluorophores for Super‐Resolution Imaging of Live Cells
Authors: Zhang Xinfu , Chen Lingcheng , Huang Zhenlong , Ling Ni , Xiao Yi
Published: December 2020

Newly emerging super‐resolution imaging techniques provide opportunities for precise observations on cellular microstructures. However, they also impose severe demands on fluorophores. Here, we develop a new series of NIR xanthene dyes, named as KRhs, by replacing the 10‐position O of rhodamines with a cyclo‐ketal. KRhs display an intense NIR emission peak at 700 nm with fluorescence quantum yields up to 0.64. More importantly, they, without the aid of enhancing buffer, exhibit stochastic fluorescence off–on switches to support time‐resolved localization of single fluorophore. KRhs are functionalized into KRh‐MitoFix, KRh‐Mem and KRh‐Halo that demonstrate mitochondria, plasma membrane and fusion protein targeting ability, respectively. Consequently, these KRh probes demonstrate straightforward usage for super‐resolution imaging of these targets in live cells. Therefore, KRhs merit future development for fluorescence labeling and super‐resolution imaging in the NIR region.
Multiple Solutions When Fitting Excess Gibbs Energy Models and Implications for Process Simulation
Authors: Vasiliu Dan , Göttl Quirin , Bröcker Sönke , Burger Jakob
Published: December 2020

Excess Gibbs energy models are often fitted to binary experimental data of phase equilibria. Even in the case of two binary parameters fitted to two binary infinite‐dilution activity coefficients, multiple solutions for the parameters may occur. The present work shows that this is also true, if more data – like vapor‐liquid equilibrium data sets – is used. Chemical systems and conditions are identified that lead to multiple solutions. It is shown that the multiple solutions may lead to significantly different results when the models are used in simulation of separation processes.
Relationship between immune checkpoint proteins, tumour microenvironment characteristics, and prognosis in primary operable colorectal cancer
Authors: Al‐Badran Sara SF , Grant Lauren , Campo Maejoy V , Inthagard Jitwadee , Pennel Kathryn , Quinn Jean , Konanahalli Prakash , Hayman Liam , Horgan Paul G , McMillan Donald C , Roxburgh Campbell SD , Roseweir Antonia , Park James H , Edwards Joanne
Published: December 2020

The tumour microenvironment is an important factor for colorectal cancer prognosis, affecting the patient's immune response. Immune checkpoints, which regulate the immune functions of lymphocytes, may provide prognostic power. This study aimed to investigate the prognostic value of the immune checkpoints TIM‐3, LAG‐3 and PD‐1 in patients with stage I–III colorectal cancer. Immunohistochemistry was employed to detect TIM‐3, LAG‐3, PD‐1 and PD‐L1 in 773 patients with stage I–III colorectal cancer. Immune checkpoint protein expression was assessed in tumour cells using the weighted histoscore, and in immune cells within the stroma using point counting. Scores were analysed for associations with survival and clinical factors. High tumoural LAG‐3 (hazard ratio [HR] 1.45 95% confidence interval [CI] 1.00–2.09, p = 0.049) and PD‐1 (HR 1.34 95% CI 1.00–1.78, p = 0.047) associated with poor survival, whereas high TIM‐3 (HR 0.60 95% CI 0.42–0.84, p = 0.003), LAG‐3 (HR 0.58 95% CI 0.40–0.87, p = 0.006) and PD‐1 (HR 0.65 95% CI 0.49–0.86, p = 0.002) on immune cells within the stroma associated with improved survival, while PD‐L1 in the tumour (p = 0.487) or the immune cells within the stroma (p = 0.298) was not associated with survival. Furthermore, immune cell LAG‐3 was independently associated with survival (p = 0.017). Checkpoint expression scores on stromal immune cells were combined into a Combined Immune Checkpoint Stromal Score (CICSS), where CICSS 3 denoted all high, CICSS 2 denoted any two high, and CICSS 1 denoted other combinations. CICSS 3 was associated with improved patient survival (HR 0.57 95% CI 0.42–0.78, p = 0.001). The results suggest that individual and combined high expression of TIM‐3, LAG‐3, and PD‐1 on stromal immune cells are associated with better colorectal cancer prognosis, suggesting there is added value to investigating multiple immune checkpoints simultaneously.
Discovery of Alternative Chemotherapy Options for Leishmaniasis through Computational Studies of Asteraceae
Authors: Herrera‐Acevedo Chonny , Perdomo‐Madrigal Camilo , Muratov Eugene N. , Scotti Luciana , Scotti Marcus Tullius
Published: December 2020

Leishmaniasis is a complex disease caused by over 20 Leishmania species that primarily affects populations with poor socioeconomic conditions. Currently available drugs for treating leishmaniasis include amphotericin B, paromomycin, and pentavalent antimonials, which have been associated with several limitations, such as low efficacy, the development of drug resistance, and high toxicity. Natural products are an interesting source of new drug candidates. The Asteraceae family includes more than 23 000 species worldwide. Secondary metabolites that can be found in species from this family have been widely explored as potential new treatments for leishmaniasis. Recently, computational tools have become more popular in medicinal chemistry to establish experimental designs, identify new drugs, and compare the molecular structures and activities of novel compounds. Herein, we review various studies that have used computational tools to examine various compounds identified in the Asteraceae family in the search for potential drug candidates against Leishmania.