bluuebunny/crossref_metadata_2025_split huggingface dataset:
Probing Neuropeptide Volume Transmission In Vivo by Simultaneous Near‐Infrared Light‐Triggered Release and Optical Sensing**
Authors: Xiong Hejian , Lacin Emre , Ouyang Hui , Naik Aditi , Xu Xueqi , Xie Chen , Youn Jonghae , Wilson Blake A. , Kumar Krutin , Kern Tyler , Aisenberg Erin , Kircher Daniel , Li Xiuying , Zasadzinski Joseph A. , Mateo Celine , Kleinfeld David , Hrabetova Sabina , Slesinger Paul A. , Qin Zhenpeng 
Published: June 2022

AbstractNeuropeptides are abundant signaling molecules in the central nervous system. Yet remarkably little is known about their spatiotemporal spread and biological activity. Here, we developed an integrated optical approach using Plasmonic nAnovesicles and cell‐based neurotransmitter fluorescent engineered reporter (CNiFER), or PACE, to probe neuropeptide signaling in the mouse neocortex. Small volumes (fL to pL) of exogenously supplied somatostatin‐14 (SST) can be rapidly released under near‐infrared light stimulation from nanovesicles implanted in the brain and detected by SST2 CNiFERs with nM sensitivity. Our measurements reveal reduced but synchronized SST transmission within 130 μm, and markedly smaller and delayed transmission at longer distances. These measurements enabled a quantitative estimation of the SST loss rate due to peptide degradation and binding. PACE offers a new tool for determining the spatiotemporal scales of neuropeptide volume transmission and signaling in the brain.
A Field‐Independent Method for the Rapid Generation of Hyperpolarized [1‐13C]Pyruvate in Clean Water Solutions for Biomedical Applications
Authors: Mamone Salvatore , Jagtap Anil P. , Korchak Sergey , Ding Yonghong , Sternkopf Sonja , Glöggler Stefan 
Published: June 2022

AbstractHyperpolarization methods in magnetic resonance enhance the signals by several orders of magnitude, opening new windows for real‐time investigations of dynamic processes in vitro and in vivo. Here, we propose a field‐independent para‐hydrogen‐based pulsed method to produce rapidly hyperpolarized13C‐labeled substrates. We demonstrate the method by polarizing the carboxylic carbon of the pyruvate moiety in a purposely designed precursor to 24 % at ≈22 mT. Following a fast purification procedure, we measure 8 % polarization on free [1‐13C]pyruvate in clean water solutions at physiological conditions at 7 T. The enhanced signals allow real‐time monitoring of the pyruvate‐lactate conversion in cancer cells, demonstrating the potential of the method for biomedical applications in combination with existing or developing magnetic resonance technologies.
Highly Active and Thermally Robust Nickel Enolate Catalysts for the Synthesis of Ethylene‐Acrylate Copolymers
Authors: Xiong Shuoyan , Hong Alexandria , Bailey Brad C. , Spinney Heather A. , Senecal Todd D. , Bailey Hannah , Agapie Theodor 
Published: June 2022

AbstractThe insertion copolymerization of polar olefins and ethylene remains a significant challenge in part due to catalysts′ low activity and poor thermal stability. Herein we demonstrate a strategy toward addressing these obstacles through ligand design. Neutral nickel phosphine enolate catalysts with large phosphine substituents reaching the axial positions of Ni achieve activity of up to 7.7×103 kg mol−1 h−1 (efficiency >35×103 g copolymer/g Ni) at 110 °C, notable for ethylene/acrylate copolymerization. NMR analysis of resulting copolymers reveals highly linear microstructures with main‐chain ester functionality. Structure‐performance studies indicate a strong correlation between axial steric hindrance and catalyst performance.
Lewis Base Catalyzed Synthesis of Sulfur Heterocycles via the C1‐Pyridinium Enolate
Authors: Cromwell Simon , Sutio Randy , Zhang Changhe , Such Georgina K. , Lupton David W. 
Published: June 2022

AbstractWhile the addition of C1‐Lewis base enolates to carbonyls and related structures are well established, the related addition to thiocarbonyls compounds are unknown. Herein, we report a reaction cascade in which a C1‐pyridinium enolate undergos addition to dithioesters, trithiocarbonates and xanthates. The reaction provides access to a range of dihydrothiophenes and dihydrothiopyrans (28‐examples). Mechanistic investigations, including isolation of intermediates, electronic correlation, and kinetic isotope effect studies support the viability of an activated acid intermediate giving rise to the C1‐pyridinium enolate which undergoes turnover limiting cyclization. Subsequent formation of a β‐thiolactone regenerates the catalyst with loss of carbon oxysulfide providing the observed products.
Precise Tailoring of Polyester Bottlebrush Amphiphiles toward Eco‐Friendly Photonic Pigments via Interfacial Self‐Assembly
Authors: Guo Qilin , Xue Runze , Zhao Jian , Zhang Yuxia , van de Kerkhof Gea T. , Zhang Kunyu , Li Yuesheng , Vignolini Silvia , Song Dong‐Po 
Published: June 2022

AbstractBiodegradable photonic microspheres with structural colors are promising substitutes to polluting microbeads and toxic dyes. Here, amphiphilic polyester‐block‐poly(ethylene glycol) bottlebrush block copolymers (BBCPs) with polylactic acid or poly(ϵ‐caprolactone) as the hydrophobic block are synthesized and used to fabricate eco‐friendly photonic pigments. Molecular parameters of BBCPs, including rigidity and symmetry, are precisely tailored by variation of side chain lengths, which enables effective manipulation of interfacial tension (γ). Organized spontaneous emulsion mechanism is enabled only whenγfalls in a suitable range (10.6–14.3 mN m−1), producing ordered water‐in‐oil‐in‐water multiple emulsions and ordered porous structures. Consequently, highly saturated and tunable structural colors are observed due to coherent light scattering from the porous structures. Such photonic materials are nontoxic as confirmed by careful safety tests using aquatic model organisms.
A Site Distance Effect Induced by Reactant Molecule Matchup in Single‐Atom Catalysts for Fenton‐Like Reactions
Authors: Wang Bingqing , Cheng Cheng , Jin Mengmeng , He Jia , Zhang Hui , Ren Wei , Li Jiong , Wang Dingsheng , Li Yadong 
Published: June 2022

AbstractUnderstanding the site interaction nature of single‐atom catalysts (SACs), especially densely populated SACs, is vital for their application to various catalytic reactions. Herein, we report a site distance effect, which emphasizes how well the distance of the adjacent copper atoms (denoted as dCu1−Cu1) matches with the reactant peroxydisulfate (PDS) molecular size to determine the Fenton‐like reaction reactivity on the carbon‐supported SACs. The optimized dCu1−Cu1 in the range of 5–6 Å, which matches the molecular size of PDS, endows the catalyst with a nearly two times higher turnover frequency than that of dCu1−Cu1 beyond this range, accordingly achieving record‐breaking kinetics for the oxidation of emerging organic contaminants. Further studies suggest that this site distance effect originates from the alteration of PDS adsorption to a dual‐site structure on Cu1−Cu1 sites when dCu1−Cu1 falls within 5–6 Å, significantly enhancing the interfacial charge transfer and consequently resulting in the most efficient catalyst for PDS activation so far.
Linker Scissoring Strategy Enables Precise Shaping of Metal–Organic Frameworks for Chromatographic Separation
Authors: Xu Ming , Cai Peiyu , Meng Sha‐Sha , Yang Yihao , Zheng De‐Sheng , Zhang Qing‐Hua , Gu Lin , Zhou Hong‐Cai , Gu Zhi‐Yuan 
Published: June 2022

AbstractPrecise shaping of metal–organic frameworks (MOFs) is significant in both fundamental coordination chemistry and practical applications, such as catalysis, separation, and biomedicine. Herein, we demonstrated a linker scissoring strategy for precisely shaping MOFs through surface conformational pairing. In this strategy, the bidentate linkers which were designed according to the original tetratopic ligands and the coordination environment of MOF surfaces, were utilized as the covering agents. The shape of these covering agents and the surface conformation of metals onto MOFs restricted them to coordinate on specific MOF facets thus precisely controlling the shape of the MOFs. Different shapes of PCN‐608 from nanoplate (PCN‐NP) to nanorod (PCN‐NR) have been targeted by adding different bidentate linkers. The universality of this strategy was demonstrated by controlling the shapes of the NU‐MOFs from nanoplate to nanorod. This strategy provides a new guiding principle to synthesize MOF nanocrystals with controlled shapes.
Deconvoluting the Optical Response of Biocompatible Photonic Pigments
Authors: Wang Zhen , Chan Chun Lam Clement , Haataja Johannes S. , Schertel Lukas , Li Ruiting , van de Kerkhof Gea T. , Scherman Oren A. , Parker Richard M. , Vignolini Silvia 
Published: June 2022

AbstractTo unlock the widespread use of block copolymers as photonic pigments, there is an urgent need to consider their environmental impact (cf. microplastic pollution). Here we show how an inverse photonic glass architecture can enable the use of biocompatible bottlebrush block copolymers (BBCPs), which otherwise lack the refractive index contrast needed for a strong photonic response. A library of photonic pigments is produced from poly(norbornene‐graft‐polycaprolactone)‐block‐poly(norbornene‐graft‐polyethylene glycol), with the color tuned via either the BBCP molecular weight or the processing temperature upon microparticle fabrication. The structure–optic relationship between the 3D porous morphology of the microparticles and their complex optical response is revealed by both an analytical scattering model and 3D finite‐difference time domain (FDTD) simulations. Combined, this allows for strategies to enhance the color purity to be proposed and realized with our biocompatible BBCP system.
A Site Distance Effect Induced by Reactant Molecule Matchup in Single‐Atom Catalysts for Fenton‐Like Reactions
Authors: Wang Bingqing , Cheng Cheng , Jin Mengmeng , He Jia , Zhang Hui , Ren Wei , Li Jiong , Wang Dingsheng , Li Yadong 
Published: June 2022

AbstractUnderstanding the site interaction nature of single‐atom catalysts (SACs), especially densely populated SACs, is vital for their application to various catalytic reactions. Herein, we report a site distance effect, which emphasizes how well the distance of the adjacent copper atoms (denoted asdCu1−Cu1) matches with the reactant peroxydisulfate (PDS) molecular size to determine the Fenton‐like reaction reactivity on the carbon‐supported SACs. The optimizeddCu1−Cu1in the range of 5–6 Å, which matches the molecular size of PDS, endows the catalyst with a nearly two times higher turnover frequency than that ofdCu1−Cu1beyond this range, accordingly achieving record‐breaking kinetics for the oxidation of emerging organic contaminants. Further studies suggest that this site distance effect originates from the alteration of PDS adsorption to a dual‐site structure on Cu1−Cu1sites whendCu1−Cu1falls within 5–6 Å, significantly enhancing the interfacial charge transfer and consequently resulting in the most efficient catalyst for PDS activation so far.
1,2,3‐Triazole rich polymers for flame retardant application: A review
Authors: Sykam Kesavarao , Donempudi Shailaja , Basak Pratyay 
Published: June 2022

AbstractDevelopment of the non‐halogenated flame retardants (FRs) is an emerging research area as halogenated FRs are prone to produce carcinogenic and persistent organic pollutants. In this context, 1,2,3‐triazole synergized FR polymeric materials noticeably attained great interest in the last decade. The mini‐review highlights the role of azide‐alkyne click chemistry with specific reference to 1,2,3‐triazole moiety covalently grafted FR for various polymeric systems. In particular, the intumescent FR mechanism of 1,2,3‐triazole has been reviewed and the technical evidence for the mechanism is provided by fourier transform infrared spectroscopy (FTIR), energy‐dispersive X‐ray spectroscopy (EDX), and X‐ray photoelectron spectroscopy (XPS) analysis. 1,2,3‐triazole moiety is increasingly proving itself to be a potent non‐halogenated FR and it has the potential to be adopted by the industry in near future.
Acrylate polymer prepared by dispersion polymerization and its crude oil emulsion demulsification performance
Authors: Wang Xiujun , Wang Naxiang , Yuan Sisi , Tang Qingqing , Wang Yifan , Fang Shenwen , Duan Ming 
Published: June 2022

AbstractThe development of a new crude oil emulsion demulsifier to replace the block polyether has always attracted attention. In this article, a novel crude oil emulsion demulsifier was prepared by dispersion polymerization using a mixture of ether and water as the dispersion medium and acrylate, methacryloxyethylthrimethyl ammonium chloride (DMC), and acrylamide as the comonomers. Taking the stability and demulsification performance as the index, the effects of acrylate type, ether/water mass ratio, monomer mass ratio, monomer concentration, initiator type, ether type, and reaction temperature on the polymerization results were investigated. The experimental results showed that when the acrylate was butyl acrylate (BA), the mass ratio of BA to DMC was 1:1, and dispersion medium was the mixture of dipropylene glycol methyl ether and water (ether/water mass ratio 1.5:1), monomer concentration was 20 wt%, initiator was V50, reaction temperature was in range of 50 to 55°C, and polymerization reaction was 10 h, the product P (BA‐DMC‐AM) had a good demulsification performance for the crude oil emulsion (crude oil density 0.9625 g/cm3, water content in emulsion 50%). When the dosage of P (BA‐DMC‐AM) was 200 mg/L and the temperature was 75°C, its dehydration was higher than 90% after demulsification for 4 h. This efficiency was similar with the block polyether demulsifier BH133. In addition, interfacial properties showed that P (BA‐DMC‐AM) can adsorb onto the oil–water interface and reduce the strength of W/O interfacial film, thereby achieving demulsification.
2022 American College of Rheumatology/American Association of Hip and Knee Surgeons Guideline for the Perioperative Management of Antirheumatic Medication in Patients With Rheumatic Diseases Undergoing Elective Total Hip or Total Knee Arthroplasty
Authors: Goodman Susan M. , Springer Bryan D. , Chen Antonia F. , Davis Marshall , Fernandez David R. , Figgie Mark , Finlayson Heather , George Michael D. , Giles Jon T. , Gililland Jeremy , Klatt Brian , MacKenzie Ronald , Michaud Kaleb , Miller Andy , Russell Linda , Sah Alexander , Abdel Matthew P. , Johnson Beverly , Mandl Lisa A. , Sculco Peter , Turgunbaev Marat , Turner Amy S. , Yates Adolph , Singh Jasvinder A. 
Published: June 2022

ObjectiveTo develop updated guidelines for the perioperative management of disease‐modifying medications for patients with rheumatic diseases, specifically those with inflammatory arthritis (IA) and those with systemic lupus erythematosus (SLE), undergoing elective total hip arthroplasty (THA) or elective total knee arthroplasty (TKA).MethodsWe convened a panel of rheumatologists, orthopedic surgeons, and infectious disease specialists, updated the systematic literature review, and included currently available medications for the clinically relevant population, intervention, comparator, and outcomes (PICO) questions. We used the Grading of Recommendations Assessment, Development and Evaluation (GRADE) methodology to rate the quality of evidence and the strength of recommendations using a group consensus process.ResultsThis guideline updates the 2017 recommendations for perioperative use of disease‐modifying antirheumatic therapy, including traditional disease‐modifying antirheumatic drugs, biologic agents, targeted synthetic small‐molecule drugs, and glucocorticoids used for adults with rheumatic diseases, specifically for the treatment of patients with IA, including rheumatoid arthritis and spondyloarthritis, those with juvenile idiopathic arthritis, or those with SLE who are undergoing elective THA or TKA. It updates recommendations regarding when to continue, when to withhold, and when to restart these medications and the optimal perioperative dosing of glucocorticoids.ConclusionThis updated guideline includes recently introduced immunosuppressive medications to help decision‐making by clinicians and patients regarding perioperative disease‐modifying medication management for patients with IA and SLE at the time of elective THA or TKA.
Variability of Primary Sjögren's Syndrome Is Driven by Interferon‐α and Interferon‐α Blood Levels Are Associated With the Class II HLA–DQ Locus
Authors: Trutschel Diana , Bost Pierre , Mariette Xavier , Bondet Vincent , Llibre Alba , Posseme Celine , Charbit Bruno , Thorball Christian W. , Jonsson Roland , Lessard Christopher J. , Felten Renaud , Ng Wan Fai , Chatenoud Lucienne , Dumortier Hélène , Sibilia Jean , Fellay Jacques , Brokstad Karl A. , Appel Silke , Tarn Jessica R. , Quintana‐Murci Lluis , Mingueneau Michael , Meyer Nicolas , Duffy Darragh , Schwikowski Benno , Gottenberg Jacques Eric ,   The Milieu Intérieur Consortium, ASSESS study investigators, and NECESSITY Consortium
Published: June 2022

ObjectivePrimary Sjögren's syndrome (SS) is the second most frequent systemic autoimmune disease, affecting 0.1% of the general population. To characterize the molecular and clinical variabilities among patients with primary SS, we integrated transcriptomic, proteomic, cellular, and genetic data with clinical phenotypes in a cohort of 351 patients with primary SS.MethodsWe analyzed blood transcriptomes and genotypes of 351 patients with primary SS who were participants in a multicenter prospective clinical cohort. We replicated the transcriptome analysis in 3 independent cohorts (n = 462 patients). We determined circulating interferon‐α (IFNα) and IFNγ protein concentrations using digital single molecular arrays (Simoa).ResultsTranscriptome analysis of the prospective cohort showed a strong IFN gene signature in more than half of the patients; this finding was replicated in the 3 independent cohorts. Because gene expression analysis did not discriminate between type I IFN and type II IFN, we used Simoa to demonstrate that the IFN transcriptomic signature was driven by circulating IFNα and not by IFNγ protein levels. IFNα protein levels, detectable in 75% of patients, were significantly associated with clinical and immunologic features of primary SS disease activity at enrollment and with increased frequency of systemic complications over the 5‐year follow‐up. Genetic analysis revealed a significant association between IFNα protein levels, a major histocompatibility (MHC) class II haplotype, and anti‐SSA antibody. Additional cellular analysis revealed that an MHC class II HLA–DQ locus acts through up‐regulation of HLA class II molecules on conventional dendritic cells.ConclusionWe identified the predominance of IFNα as a driver of primary SS variability, with IFNα demonstrating an association with HLA gene polymorphisms.
Theoretical Investigation of Switch Effect on the Efficiency and Adaptivity of Molecular Optoelectronic Conversion Devices
Authors: Jiao Fangfang , Wei Mingzhi , Leng Jiancai , Song Ziyue , Hu Wei , Zhang Yujin 
Published: June 2022

AbstractMolecular photoswitch can effectively regulate charge separation (CS) and charge recombination (CR) in donor‐acceptor (D‐A) systems. However, deformation of the donor‐switch‐acceptor (D‐S‐A) systems caused by the switch isomerization will destroy the geometrical stability of the battery. Here we take the planar platinum(II) terpyridyl complex of [Pt(tBu3tpy)(−C≡C−Ph)n]+ as the typical D‐A model, designed six D‐S‐A systems using different photoswitches (dimethyldihydropyrene, fulgimide, arylazopyrazole, N‐salicylideneaniline, spiropyran, and dithienylethene, denoted as D‐S‐A 1–6 hereafter). Our investigations show that the D‐S‐A 1–6 can absorb visible light of 799 nm, 673 nm, 527 nm, 568 nm, 616 nm, and 629 nm, facilitating electrons transfer from the donor and the switch to the acceptor through the Switch‐on channel. Then cationic character of the photoswitch can undergo much more rapid isomerization than the neutral form due to the lower energy barrier. The Switch‐off isomer breaks the conjugation of the D‐S‐A system, effectively turning off the CT channel and forming the CS state. Based on the evaluated conjugated backbone twist (CBT) angle, we found that D‐S‐A 1, 2, 4, 6 exhibit little configurational change and can be good candidates as the organic solar cell. The proposed D‐S‐A design controlled by the molecular switch may help to develop a solution for solar‐harvesting practical applications.
Combined MD and QM/MM Calculations Reveal Allostery‐Driven Promiscuity in Dipeptide Epimerases of Enolase Family
Authors: Tripathi Ankita , Dutta Dubey Kshatresh 
Published: June 2022

AbstractThe adaptability of the active site to amplify the secondary function is supposed to be the fundamental cause of the promiscuity and the evolution of new functions in enzymes. In most cases, mutations occur close to the active site and/or in the catalytic site to change the active site plasticity to accommodate the non‐native substrate. In the present study, using MD simulations and hybrid QM/MM calculations, we have shown a way to enhance the promiscuity, i. e., the allostery‐driven promiscuity. Using a case study of the AEE enzyme where the capping loop recognizes the substrate, herein, we show that a single site mutation (D321G) far from the capping loop can induce a large conformational change in the capping loop to recognize different substrates for different functions. The QM/MM calculations for the WT and mutated enzyme provide a first validation of the mechanism of 1,1‐proton transfer and dehydration by the AEE enzyme. Since AEE epimerase possesses a highly conserved TIM‐barrel fold, we believe that our study provides a crucial lead to understanding the mechanism of emergence of secondary function which can be useful to repurpose ancient enzymes for modern usage.
AuPt bimetal‐codecorated ZnO nanowire‐based hydrogen sensors for detecting low concentration hydrogen gas with high response and selectivity
Authors: Min Sung‐Ki , Kim Hongseok , Kim Yunsu , Chang Sung‐Pil 
Published: June 2022

AbstractZnO nanowires decorated with bimetallic AuPt nanoparticles were synthesized using the vapor–liquid–solid method, followed by sputtering and thermal annealing, to fabricate highly sensitive and selective sensors for detecting ppb scale hydrogen gas. The proposed sensor demonstrated a clear pattern enough to recognize, even for 100 ppb hydrogen gas. The sensing responses of the pristine and AuPt bimetal‐codecorated ZnO nanowire‐based sensors were 1.09 and 7.3 for 100 ppb hydrogen gas, respectively. The sensing response of the proposed sensor is seven times as the decoration of AuPt nanoparticles. Furthermore, the proposed sensor exhibited excellent sensing selectivity for various interfering gases including ethanol, acetone, toluene, CO, and H2S. The proposed sensor shows excellent sensing performance because of synergistic effect of decorated AuPt, which play the role of catalysts. Therefore, hydrogen sensors showing superior sensing performance can be fabricated using this nanomaterial, and its advanced sensing performances are analyzed in this study.