bluuebunny/crossref_metadata_2025_split huggingface dataset:
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

AbstractSite‐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

AbstractMaterialien 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

AbstractThe 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

AbstractChemical 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

AbstractThe 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

AbstractReported 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

AbstractMaterials 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

AbstractThe 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

AbstractWe 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

AbstractAlthough 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

AbstractTwo 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

AbstractAutotrophic 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

AbstractBackgroundThe 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.MethodsUsing 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.ResultsSeventeen 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.ConclusionsWe present a preliminary anatomic model of the default mode network. Further studies may refine this model with the ultimate goal of clinical application.
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

AbstractIntroductionChronic 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.MethodsThis 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.ResultsOf 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).ConclusionAmong 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

AbstractPachydermoperiostosis, 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

AbstractThis 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

AbstractImproved 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

AbstractThe 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

AbstractPhenylacetylene 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.