bluuebunny/crossref_metadata_2025_split huggingface dataset:
Acridine Orange Hemi(Zinc Chloride) Salt as a Lewis Acid‐Photoredox Hybrid Catalyst for the Generation of α‐Carbonyl Radicals
Authors: Das Sanju , Mandal Tanumoy , De Sarkar Suman 
Published: November 2021

AbstractA readily accessible organic‐inorganic hybrid catalyst is reported for the reductive fragmentation of α‐halocarbonyl compounds. The robust hybrid catalyst is a self‐stabilizing combination of ZnCl2 Lewis acid and acridine orange as the photoactive organic dye. Mechanistic specifics of this hybrid catalyst have been studied in detail using both photophysical and electrochemical experiments. A systematic study enabled the discovery of the appropriate Lewis acid for the effective LUMO stabilization of α‐halocarbonyl compounds and thereby lowering of reduction potential within the range of a standard organic dye. This strategy resolves the issues like dehalogenative hydrogenation or homo‐coupling of alkyl radicals by guiding the photoredox cycle through an oxidative quenching pathway. The cooperativity between the photoactive organic dye and the Lewis acid counterparts empowers functionalization with a wide range of coupling partners through efficient and controlled generation of alkyl radicals and serves as an appropriate alternative to the expensive late transition metal‐based photocatalysts. To demonstrate the application potential of this cooperative catalytic system, four different synthetic transformations of α‐carbonyl bromides were explored with broad substrate scopes.magnified image
Transition‐Metal‐Catalyzed Cross‐Coupling and Sequential Reactions of Azides with Isocyanides
Authors: Zhang Zhen , Tan Pengpeng , Chang Wenxu , Zhang Zhenhua 
Published: November 2021

AbstractTransition‐metal‐catalyzed cross‐coupling reaction of azides with isocyanides, as a new type of nitrene transformation, has become an expeditious method to prepare carbodiimides. Considering the compatibility of this coupling process with other systems, transition‐metal‐catalyzed sequential reactions have become more popular in recent years. These remarkable advances not only involve many interesting reaction processes, but also provide useful strategies for the construction of nitrogen‐containing structures, such as guanidines, amidines, isoureas, and heterocyclic compounds. This review will present a comprehensive picture of the development of transition‐metal‐catalyzed coupling process of azides with isocyanides and their applications in the preparation of nitrogen‐containing compounds. Catalytic coupling reactions followed by nucleophilic additions will be briefly introduced here. Most recent advances in catalytic cascade reactions involving a coupling process will be highlighted and make up the main part of this review.magnified image
Multilayer Lateral Heterostructures of Van Der Waals Crystals with Sharp, Carrier–Transparent Interfaces
Authors: Sutter Eli , Unocic Raymond R. , Idrobo Juan‐Carlos , Sutter Peter 
Published: November 2021

AbstractResearch on engineered materials that integrate different 2D crystals has largely focused on two prototypical heterostructures: Vertical van der Waals stacks and lateral heterostructures of covalently stitched monolayers. Extending lateral integration to few layer or even multilayer van der Waals crystals could enable architectures that combine the superior light absorption and photonic properties of thicker crystals with close proximity to interfaces and efficient carrier separation within the layers, potentially benefiting applications such as photovoltaics. Here, the realization of multilayer heterstructures of the van der Waals semiconductors SnS and GeS with lateral interfaces spanning up to several hundred individual layers is demonstrated. Structural and chemical imaging identifies {110} interfaces that are perpendicular to the (001) layer plane and are laterally localized and sharp on a 10 nm scale across the entire thickness. Cathodoluminescence spectroscopy provides evidence for a facile transfer of electron‐hole pairs across the lateral interfaces, indicating covalent stitching with high electronic quality and a low density of recombination centers.
Respiratory manifestations in the Ehlers–Danlos syndromes
Authors: Bascom Rebecca , Dhingra Radha , Francomano Clair A. 
Published: November 2021

AbstractPersons with the Ehlers–Danlos syndromes (EDS) report a wide range of respiratory symptoms, most commonly shortness of breath, exercise limitation, and cough. Also reported are noisy breathing attributed to asthma, difficulty with deep inhalation, and inspiratory thoracic pain. The literature consists of case reports and small cross‐sectional and cohort studies. One case–control study estimated twofold to threefold greater respiratory disease burden among persons with EDS as compared to controls. The differential diagnosis for symptoms is broad. Structural alterations include pectus deformities, scoliosis, recurrent rib subluxations, and tracheobronchomalacia, associated with varying degrees of physiologic impairment. Those with vascular EDS have an increased risk of pneumothorax, intrapulmonary bleeding, cysts, and nonmalignant fibrous nodules. Functional aerodigestive manifestations such as inducible laryngeal obstruction may be misdiagnosed as asthma, with gastro‐esophageal dysmotility and reflux as common contributing factors. Inflammatory manifestations include costochondritis, bronchiectasis, and localized respiratory allergic and nonallergic mast cell activation. Cranio‐cervical instability can dysregulate respiratory control pathways. There is a need for careful phenotyping using standardized clinical tools and patient‐reported outcomes and continuing collaboration with aerodigestive specialists including otolaryngologists and gastroenterologists. Also needed is further evaluation of respiratory symptoms in persons with hypermobility spectrum disorders. Personalized monitoring strategies are invaluable for interpretation and long‐term management of respiratory symptoms.
Sample preparation for the analysis of key metabolites from cannabinoids biosynthesis in phytoplankton using gas chromatography–mass spectrometry
Authors: Ye Liyun , Budge Suzanne M. 
Published: November 2021

AbstractCannabinoids biosynthesis in phytoplankton has attracted much attention due to the rapid development of genetic tools and the optimization of genetic transformation methods in microalgae. To monitor the biosynthesis process, proper sample preparation and practical instrumental methods are needed to measure the various precursors, intermediates, cannabinoids, and their degradation products. The objective of this study was to develop a sample preparation procedure for the quantification of olivetolic acid (OA), cannabigerolic acid (CBGA), cannabidiolic acid (CBDA), tetrahydrocannabinolic acid (THCA), olivetol (OL), cannabidiol (CBD), and tetrahydrocannabinol (THC) using single‐quadrupole gas chromatography–mass spectrometry (GC–MS). Isochrysis galbana was used as the model matrix. After methanol extraction, samples were purified using solid phase extraction (SPE), silylated with N‐methyl‐N‐(trimethylsilyl)trifluoroacetamide, and analyzed using GC–MS in electron ionization mode. A strong anion‐exchange SPE efficiently recovered OA, CBGA, CBDA, and THCA. A graphitized carbon black SPE was necessary to purify OL, CBD, and THC. Both columns removed amino acids, sugars, polyols, and pigments from the algae extract and prepared samples that are suitable for silylation and GC–MS analysis. The total protocol, including solvent extraction, SPE, silylation, and GC–MS analysis, was validated in accordance with the ICH guidelines. Performance characteristics of our method are superior to existing protocols with similar complexity in the literature.
Silver‐coated conductive composite fabric with flexible, anti‐flaming for electromagnetic interference shielding
Authors: Li Ting‐Ting , Wang Xiaomeng , Wang Yanting , Shiu Bing‐Chiuan , Peng Hao‐Kai , Lou Ching‐Wen , Lin Jia‐Horng 
Published: November 2021

AbstractWith the development of modern electronic technology, there is an urgent need to prepare multifunctional polymer composite materials with flame retardant and electromagnetic shielding functions. Herein, use the chemical activity of polydopamine (PDA) to modify polyphenylene (PP) fabric to enhance its interface compatibility. Then, the dipping method was used to achieve the successful deposition of Ag nanoparticles on the surface of the PP non‐woven fabric, and by adjusting the concentration of the Ag precursor and the immersion time of the flame retardant constructed a conductive composite material with lightweight, flexible and has good flame retardant properties. The results showed that when the concentration of AgNO3 solution was 2% and the thickness was 0.166 mm, the average shielding effectiveness shielding effectiveness (SE) and SSE/t of the composite fabric reached 25.01 dB and 6097.56 dB cm2g−1, respectively. In particular, the composite fabric still maintained stable electrical conductivity after flame retardant treatment, and the average shielding effectiveness SE and SSE/t of the composite fabric reached 20.20 dB and 1518.80 dB cm2 g−1. The multifunctional conductive composite fabric prepared in this study has broad development prospects in the fields of electromagnetic shielding and smart wear.
Using MVDA with stoichiometric balances to optimize amino acid concentrations in chemically defined CHO cell culture medium for improved culture performance
Authors: Salim Taha , Chauhan Gaurav , Templeton Neil , Ling Wai Lam W. 
Published: November 2021

AbstractChemically defined (CD) media are routinely used in the production of biologics in Chinese hamster ovary (CHO) cell culture and provide enhanced raw material control. Nutrient optimized CD media is an important path to increase cell growth and monoclonal antibody (mAb) productivity in recombinant CHO cell lines. However, nutrient optimization efforts for CD media typically rely on multifactorial and experimental design of experiment approaches or complex mathematical models of cellular metabolism or gene expression systems. Moreover, the majority of these efforts are aimed at amino acids since they constitute essential nutrients in CD media as they directly contribute to biomass and protein production. In this study, we demonstrate the utilization of multivariate data analytics (MVDA) coupled with amino acid stoichiometric balances (SBs) to increased cell growth and mAb productivity in efforts to support CD media development efforts. SBs measure the difference between theoretical demand of amino acids and the empirically measured fluxes to identify various catabolic or anabolic states of the cell. When coupled with MVDA, the statistical models were not only able to highlight key amino acids toward cell growth or productivity, but also provided direction on metabolic favorability of the amino acid. Experimental validation of our approach resulted in a 55% increase in total cell growth and about an 80% increase in total mAb productivity. Increased specific consumption of stoichiometrically balanced amino acids and decreased specific consumption of glucose was also observed in optimized CD media suggesting favorable consumption of desired nutrients and a potential for energy redistribution toward increased cellular growth and mAb productivity.
Application of journey maps to the development of emergent sustainability‐oriented technologies: Lessons for user involvement in agriculture
Authors: Moretti Débora Monteiro , Baum Chad M. , Wustmans Michael , Bröring Stefanie 
Published: November 2021

AbstractThis article foregrounds the challenges and necessity of promoting user involvement in traditional sectors, especially those that constitute strong pillars for sustainable development. As a case in point, the emergence of precision agriculture technologies requires novel methods to integrate users in innovation processes. Accordingly, this article discusses three applications of journey maps developed in collaboration with users and other stakeholders in the context of agriculture. We illustrate how design‐thinking tools such as journey maps offer the means to explore user experiences, spotting previously unknown needs or problems, generate value propositions with meaning and relevance, and foresee implementation issues not directly related to the technology in focus. This research, thus, contributes by first describing applications of journey maps which are relevant for traditional sectors that are undergoing disruption, and second, by highlighting the broader usefulness of such tools for facilitating coordination among the diverse actors who are ultimately central to innovation adoption and success.
Metal‐HisTag coordination for remote loading of very small quantities of biomacromolecules into PLGA microspheres
Authors: Albert Jason , Chang Rae Sung , Garcia George A. , Schwendeman Steven P. 
Published: November 2021

AbstractChallenges to discovery and preclinical development of long‐acting release systems for protein therapeutics include protein instability, use of organic solvents during encapsulation, specialized equipment and personnel, and high costs of proteins. We sought to overcome these issues by combining remote‐loading self‐healing encapsulation with binding HisTag protein to transition metal ions. Porous, drug‐free self‐healing microspheres of copolymers of lactic and glycolic acids with high molecular weight dextran sulfate and immobilized divalent transition metal (M2+) ions were placed in the presence of proteins with or without HisTags to bind the protein in the pores of the polymer before healing the surface pores with modest temperature. Using human serum albumin, insulin‐like growth factor 1, and granulocyte‐macrophage colony‐stimulating factor (GM‐CSF), encapsulated efficiencies of immunoreactive protein relative to nonencapsulation protein solutions increased from ~41%, ~23%, and ~9%, respectively, without Zn2+ and HisTags to ~100%, ~83%, and ~75% with Zn2+ and HisTags. These three proteins were continuously released in immunoreactive form over seven to ten weeks to 73%–100% complete release, and GM‐CSF showed bioactivity >95% relative to immunoreactive protein throughout the release interval. Increased encapsulation efficiencies were also found with other divalent transition metals ions (Co2+, Cu2+, Ni2+, and Zn2+), but not with Ca2+. Ethylenediaminetetraacetic acid was found to interfere with this process, reverting encapsulation efficiency back to Zn2+‐free levels. These results indicate that M2+‐immobilized self‐healing microspheres can be prepared for simple and efficient encapsulation by simple mixing in aqueous solutions. These formulations provide slow and continuous release of immunoreactive proteins of diverse types by using a amount of protein (e.g., <10 μg), which may be highly useful in the discovery and early preclinical development phase of new protein active pharmaceutical ingredients, allowing for improved translation to further development of potent proteins for local delivery.
Developing odontoma arising from calcifying odontogenic cyst: A case report
Authors: Moradzadeh Khiavi Monir , Mahdavi Nazanin , Awudu Asoma 
Published: November 2021

AbstractDeveloping odontoma is a rare mixed odontogenic tumor that can arise with other odontogenic lesions. The association of COC with ameloblastic fibro‐odontoma is extremely rare. We report an extremely rare case of developing odontoma arising from a calcifying odontogenic cyst in a 17‐year‐old girl.
Optimization of a technology‐supported physical activity promotion intervention for breast cancer survivors: Results from Fit2Thrive
Authors: Phillips Siobhan M. , Penedo Frank J. , Collins Linda M. , Solk Payton , Siddique Juned , Song Jing , Cella David , Courneya Kerry S. , Ackermann Ronald T. , Welch Whitney A. , Auster‐Gussman Lisa A. , Whitaker Madelyn , Cullather Erin , Izenman Emily , Spring Bonnie 
Published: November 2021

BackgroundThe benefits of moderate to vigorous physical activity (MVPA) for breast cancer survivors are well established. However, most are insufficiently active. Fit2Thrive used the Multiphase Optimization Strategy methodology to determine the effect of 5 intervention components on MVPA in this population.MethodsTwo hundred sixty‐nine participants (mean age, 52.5 years; SD, 9.9 years) received a core intervention (the Fit2Thrive self‐monitoring app and Fitbit) and were randomly assigned to 5 intervention components set to on/off in a full factorial experiment: support calls, deluxe app, buddy, online gym, and text messages. The intervention was delivered over 12 weeks with a 12‐week follow‐up. MVPA was measured via accelerometry at the baseline (T1), at 12 weeks (T2), and at 24 weeks (T3). The main effects and interaction effects at each time point were examined for all components.ResultsTrial retention was high: 91.8% had valid accelerometer data at T2 or T3. Across all conditions, there were significant increases in MVPA (+53.6 min/wk; P < .001) and in the proportion of survivors meeting MVPA guidelines (+22.3%; P < .001) at T2 that were maintained but attenuated at T3 (MVPA, +24.6 min/wk; P < .001; meeting guidelines, +12.6%; P < .001). No individual components significantly improved MVPA, although increases were greater for the on level versus the off level for support calls, buddy, and text messages at T2 and T3.ConclusionsThe Fit2Thrive core intervention (the self‐monitoring app and Fitbit) is promising for increasing MVPA in breast cancer survivors, but the components provided no additional increases in MVPA. Future research should evaluate the core intervention in a randomized trial and determine what components optimize MVPA behaviors in breast cancer survivors.
Order‐Unity 13C Nuclear Polarization of [1‐13C]Pyruvate in Seconds and the Interplay of Water and SABRE Enhancement
Authors: Adelabu Isaiah , TomHon Patrick , Kabir Mohammad S. H. , Nantogma Shiraz , Abdulmojeed Mustapha , Mandzhieva Iuliia , Ettedgui Jessica , Swenson Rolf E. , Krishna Murali C. , Theis Thomas , Goodson Boyd M. , Chekmenev Eduard Y. 
Published: November 2021

AbstractSignal Amplification By Reversible Exchange in SHield Enabled Alignment Transfer (SABRE‐SHEATH) is investigated to achieve rapid hyperpolarization of 13C1 spins of [1‐13C]pyruvate, using parahydrogen as the source of nuclear spin order. Pyruvate exchange with an iridium polarization transfer complex can be modulated via a sensitive interplay between temperature and co‐ligation of DMSO and H2O. Order‐unity 13C (>50 %) polarization of catalyst‐bound [1‐13C]pyruvate is achieved in less than 30 s by restricting the chemical exchange of [1‐13C]pyruvate at lower temperatures. On the catalyst bound pyruvate, 39 % polarization is measured using a 1.4 T NMR spectrometer, and extrapolated to >50 % at the end of build‐up in situ. The highest measured polarization of a 30‐mM pyruvate sample, including free and bound pyruvate is 13 % when using 20 mM DMSO and 0.5 M water in CD3OD. Efficient 13C polarization is also enabled by favorable relaxation dynamics in sub‐microtesla magnetic fields, as indicated by fast polarization buildup rates compared to the T1 spin‐relaxation rates (e. g., ∼0.2 s−1 versus ∼0.1 s−1, respectively, for a 6 mM catalyst‐[1‐13C]pyruvate sample). Finally, the catalyst‐bound hyperpolarized [1‐13C]pyruvate can be released rapidly by cycling the temperature and/or by optimizing the amount of water, paving the way to future biomedical applications of hyperpolarized [1‐13C]pyruvate produced via comparatively fast and simple SABRE‐SHEATH‐based approaches.
Single Crystal Preparation and Luminescent Properties of Lu2O3:Eu Scintillator by Vertical Bridgman Method
Authors: Zheng Jiaqian , Liu Changjiang , Yu Haihang , Chen Lu , Yang Mei , Zhao Hengyu , Lu Baoqi , Yang Fan , Feng He 
Published: November 2021

AbstractEuropium‐doped lutetium oxide (Lu2O3:Eu) single crystal is grown by vertical Bridgman method for the first time. Correlated measurements of X‐ray diffraction, X‐ray fluorescence spectra, optical transmittance, photoluminescence excitation, photoluminescence (PL), PL decay, and X‐ray excited luminescence (XEL) spectra are performed. The transmittance of about 80% above 300 nm indicates that the crystal is of good optical quality. By measuring actual Eu3+ concentration, the effective segregation coefficient of Eu3+ in the Lu2O3:Eu crystal is calculated to be 0.75. In the PL spectrum, the dominant emission peaks at 612 and 630 nm originate from the 5D0→7F2 transitions of Eu3+ in C2 site. It is worth mentioning that several emission peaks between 575 and 605 nm mainly ascribe to the transitions of different 5D0 levels to the split 7F1 levels of Eu(C2) or Eu(C3i). PL decay spectra indicate the decay time of 612 nm emission can be determined about 1.0 ms. The decay curve of 582.6 nm emission can be fitted into triple components, and the 5.3 and 1.4 ms components are attributed to Eu3+(C3i) and Eu3+(C2), respectively. The XEL strongest emission of Lu2O3:Eu sample is around 612 nm with a bright red luminescence that matches silicon photodetectors sensitivity.
Single‐Atomic Ruthenium Active Sites on Ti3C2 MXene with Oxygen‐Terminated Surface Synchronize Enhanced Activity and Selectivity for Electrocatalytic Nitrogen Reduction to Ammonia
Authors: Chen Gang , Ding Mingmei , Zhang Kai , Shen Zhen , Wang Yueting , Ma Jun , Wang Ao , Li Yiping , Xu Hang 
Published: November 2021

AbstractDownsizing the catalyst to atom scale offers an effective way to maximize the atom utilization efficiency for electrocatalytic nitrogen reduction reaction (NRR). Herein, single‐atomic ruthenium (Ru) anchored on a chemically activated Ti3C2 with O‐terminated groups (Ti3C2O) was designed to catalyze the NRR process. The catalyst achieved a superior activity and selectivity with ammonia yield rate of 27.56 μg h−1 mg−1 and faradaic efficiency of 23.3 % at a low potential of −0.20 V versus the reversible hydrogen electrode. According to the atomic resolution images from aberration‐corrected scanning transmission electron microscopy, Ru sites on Ti3C2O achieved good dispersion on atomic scale. X‐ray photoelectron spectroscopy analysis further demonstrated that the O‐termination groups were successfully activated. Density functional theory calculations combined with experiments revealed that single Ru sites binding to four oxygen were the main reaction centers that permitted the hydrogenation of *NNH2 to *NHNH2 in a novel distal/alternating hybrid path while reducing the energy barrier of the potential‐limiting step to 0.78 eV from 0.96 eV in the distal path alone or 1.18 eV in the alternating path alone, thereby significantly promoting the NRR dynamics.
Midfrontal theta oscillations and conflict monitoring in children and adults
Authors: Chevalier Nicolas , Hadley Lauren V. , Balthrop Kullen 
Published: November 2021

AbstractConflict monitoring is central in cognitive control, as detection of conflict serves as a signal for the need to engage control. This study examined whether (1) midfrontal theta oscillations similarly support conflict monitoring in children and adults, and (2) performance monitoring difficulty influences conflict monitoring and resolution. Children (n = 25) and adults (n = 24) completed a flanker task with fair or rigged response feedback. Relative to adults, children showed a smaller congruency effect on midfrontal theta power, overall lower midfrontal theta power and coherence, and (unlike adults) no correlation between midfrontal theta power and N2 amplitude, suggesting that reduced neural communication efficiency contributes to less efficient conflict monitoring in children than adults. In both age groups, response feedback fairness affected response times and the P3, but neither midfrontal theta oscillations nor the N2, indicating that performance monitoring difficulty influenced conflict resolution but not conflict monitoring.