bluuebunny/crossref_metadata_2025_split huggingface dataset:
Controllable Macroscopic Chirality of Coordination Polymers through pH and Anion‐Mediated Weak Interactions
Authors: Wu Lan‐Qing , Xu Yan , Hou Ting , Jia Jia‐Ge , Huang Xin‐Da , Weng Guo‐Guo , Bao Song‐Song , Zheng Li‐Min 
Published: October 2021

AbstractHelical architectures with controllable helical sense bias have recently attracted considerable interest for mimicking biological helices and developing novel chiral materials. Coordination polymers (CPs), composed of metal ion nodes and organic linkers, are intriguing systems showing tunable structures and functions. However, CPs with helical morphologies have rarely been explored so far. Particularly, chirality inversion through external stimulus has not been achieved in helical CPs. In this work, we carried out an in‐depth investigation on the self‐assembly of 1D gadolinium(III) phosphonate CPs using GdX3 (X=Cl, Br, I) and Gd(RSO3) (R=CH3, C6H5, CF3) as metal sources and R‐(1‐phenylethylamino)methyl phosphonic acid (R‐pempH2) as ligand. Superhelices were formed by precise control of the interchain interactions through different intercalated anions. Furthermore, the twisting direction of superhelices could be controlled by synergistic effect of anions and pH. This study may provide a new route to fabricate helical nanostructures of CPs with a desirable chiral sense and help understand the inner mechanism of the self‐assembly process of macroscopic helical structures of molecular systems.
Fluorination Reactions at a Platinum Carbene Complex: Reaction Routes to SF3, S(=O)F and Fluorido Complexes
Authors: Dirican Dilcan , Talavera Maria , Braun Thomas 
Published: October 2021

AbstractThe electron‐rich Pt complex [Pt(IMes)2] (IMes: [1,3‐bis(2,4,6‐trimethylphenyl)‐2‐imidazolinylidine]) can be used as precursor for the syntheses of a variety of fluorido ligand containing compounds. The sulfur fluoride SF4 undergoes a rapid oxidative addition at Pt0 to yield trans‐[Pt(F)(SF3)(IMes)2]. A photolytic reaction of SF6 at [Pt(IMes)2] in the presence of IMes gave the fluorido complexes trans‐[Pt(F)2(IMes)2] and trans‐[Pt(F)(SF3)(IMes)2] along with trans‐[Pt(F)(SOF)(IMes)2] and trans‐[Pt(F)(IMes’)(IMes)] (IMes’: cyclometalated IMes ligand), the latter being products produced by reaction with adventitious water. trans‐[Pt(F)(SOF)(IMes)2] and trans‐[Pt(F)2(IMes)2] were synthesized independently by treatment of [Pt(IMes)2] with SOF2 or XeF2. A reaction of [Pt(IMes)2] with a HF source gave trans‐[Pt(H)(F)(IMes)2], and an intermediate bifluorido complex trans‐[Pt(H)(FHF)(IMes)2] was identified. Compound trans‐[Pt(H)(F)(IMes)2] converts in the presence of CsF into trans‐[Pt(F)(IMes’)(IMes)].
Development of an electrochemical flow‐through cell for the fast and easy generation of isotopically labeled metabolite standards
Authors: Göldner Valentin , Fangmeyer Jens , Karst Uwe 
Published: October 2021

AbstractIn drug development, metabolite standards of new chemical entities are required for a comprehensive safety evaluation. Stable isotope‐labeled internal metabolite standards at the milligram scale, which are difficult and expensive to synthesize in common bottom‐up approaches, are necessary for metabolite quantification using liquid chromatography/mass spectrometry. A preparative electrochemical flow‐through cell is presented here as a powerful tool for the cheap and straightforward synthesis of milligram amounts of isotopically labeled metabolite standards. The developed cell scales up established, so‐called “coulometric” electrochemical cells. Problems like electrode fouling and cross contamination between syntheses are addressed by the use of exchangeable working electrodes. The applicability of the developed cell for the synthesis of metabolite standards is demonstrated using isotopically labeled acetaminophen as a model system for the generation of a biologically relevant phase II metabolite.
Determination of ghrelin and desacyl ghrelin in human plasma and urine by means of LC–MS/MS for doping controls
Authors: Thomas Andreas , Krombholz Sophia , Wolf Carina , Thevis Mario 
Published: October 2021

AbstractThe hunger hormone ghrelin (G) is classified as prohibited substance in professional sport by the World Anti‐Doping Agency (WADA), due to its known growth hormone releasing properties. The endogenous bioactive peptide consists of 28 amino acids with a caprylic acid attached to serine at position 3. Within this study, it was aimed to develop methods to determine G and desacyl ghrelin (DAG) in plasma and urine by means of LC–MS/MS. Two strategies were applied with a bottom‐up approach for plasma and top‐down analyses for urine. Both sample preparation procedures were based on solid‐phase extraction for enrichment and sample clean‐up. Method validation showed good results for plasma and urine with limits of detection (LODs) for G and DAG between 30 and 50 pg/ml, recoveries between 45–50%, and imprecisions (intra‐ and inter‐day) between 3% and 24%. Plasma analysis was also valid for quantification with accuracies determined with ~100% for G and ~106% for DAG. The minimum required performance level for doping control laboratories is set to 2 ng/ml in urine, and the herein established method yielded acceptable results even at 5% of this level. As proof‐of‐concept, plasma levels (G and DAG) of healthy volunteers were determined and ranged between 30 and 100 pg/ml for G and 100–1200 pg/ml for DAG. In contrast to earlier reported studies using ligand binding assays for urinary G and DAG, in this mass spectrometry‐based study, no endogenous urinary G and DAG were found, although the LODs should enable this.
Enhanced Hydrogen Evolution Catalysis from Hierarchical Nanostructure Co−P@CoMo−P Electrode
Authors: Han Dongdong , Xie Yufang , Wu Yishang , Xu Kangli , Qian Yitai 
Published: October 2021

AbstractThe construction of hierarchical nanostructures is a fascinating target because of their promising applications in electronic analysis and catalysis. Herein, we establish a 3‐d hierarchical nanostructure Co−P@CoMo−P to enhance the catalytic ability. The hydrogen evolution reaction catalytic ability was enhanced significantly with a Tafel slope of 34 mV dec−1 and an overpotential of 37 mV to achieve 10 mA cm−2, which are superior to that of recently reported non‐noble metal catalysts. The high catalytic performance could be rationalized as follows: (1) Co−P nanowire intimately contacted with Ni foam enables good mechanical adhesion and facilitates the flow of electrons from Ni foam to CoMo−P nanosheet; (2) the hierarchical nanostructure can expose more active sites and transport reactants and products sufficiently; (3) the space between two separate hierarchical nanostructures is loose and open, allowing electrolyte to diffuse into all the active sites and make them used efficiently. This work is promising for the development of novel non‐noble metal catalysts for energy technologies.
Thioether‐Containing Copper Complexes as PHM, DβM, and TβM Model Systems
Authors: Gómez‐Vidales Virginia , Castillo Ivan 
Published: October 2021

AbstractThis minireview presents efforts of synthetic chemists to mimic the active site of the copper monooxygenase enzymes peptidylglycine α‐hydroxylating monooxygenase (PHM), dopamine β‐monooxygenase (DβM), and tyramine β‐monooxygenase (TβM), all of which feature copper‐thioether ligation in their resting states. These monooxygenases are involved in the initial activation of O2 to generate neurotransmitters by the selective activation of C−H bonds of their corresponding substrates, resulting in subsequent hydroxylation. Attempts to emulate the N2S donor set provided by the two histidines and the methionine residues that coordinate to copper in the active site employ N2S and N3S‐type ligands, with the latter ones providing the best conditions for testing the reactivity of their CuI complexes with dioxygen. Identification of CuII‐superoxos as capable agents for C−H activation has provided support for these species as the key reactive intermediates in the enzymatic systems. Synthetic end‐on [CuII‐η1‐O2.−] and side‐on [CuII‐η2‐O2.−] cupric superoxos are capable of such transformations, which is related to the open question of whether the methionine S‐donor may act as a hemilabile ligand in biological systems.
Passerini and Ugi Reactions Involving Kinetically Unstable Isocyanides
Authors: Quelhas Alexandre , Gazzeh Houda , Roisnel Thierry , Trolez Yann , Guillemin Jean‐Claude 
Published: October 2021

AbstractKinetically unstable isocyanides as vinyl, allenyl and propargyl isocyanides react in Passerini and Ugi reactions faster than they decompose and lead to functionalized α‐acyloxy amides and α‐amino amides, respectively, which can subsequently be used in reactions involving the unsaturated substituent.
Electrochemical Immunosensor for the Sensitive Detection of Alzheimer's Biomarker Amyloid‐β (1–42) Using the Heme‐amyloid‐β (1–42) Complex as the Signal Source
Authors: Ding Minling , Shu Qi , Zhang Nan , Yan Chaoren , Niu Huizhe , Li Xiaoqian , Guan Ping , Hu Xiaoling 
Published: October 2021

AbstractThe amyloid‐β peptide (1–42) (Aβ42) can provide high diagnostic accuracy for the early diagnosis of Alzheimer's disease (AD). In this study, an immunosensor based on the peroxidase‐like activity of heme‐Aβ42 was designed for Aβ42 detection. The glassy carbon electrode (GCE) was electrodeposited Au particles (GCE/Au). The GCE/Au was modified using polythionine‐methylene blue (PTH−MB), AuNPs, monoclonal antibody (anti‐Aβ42), and bovine serum albumin (BSA), successively. The GCE/Au/PTH−MB/AuNPs/anti‐Aβ42/BSA could competitively recognize Aβ42 and heme‐Aβ42. The anchored heme‐Aβ42 showed strong electrocatalytic activity between H2O2 and ferrocenemethanol. Under optimum conditions, we determined detection limits of 17.3 pM in PBS pH 7, 25.2 pM in serum, and 23.8 pM in saliva. The recovery ranged from 71.0 % to 117.8 %.
Carbon stocks in umbric ferralsols driven by plant productivity and geomorphic processes, not by mineral protection
Authors: Martinez Pedro , Silva Lucas C. R. , Calegari Marcia Regina , de Camargo Plinio Barbosa , Vidal‐Torrado Pablo , Kleber Markus 
Published: October 2021

AbstractUmbric ferralsols (UF) have organic carbon stocks within the first 1 m of soil profile depth that are nearly double the size (~19 kg C m−2) compared to the average carbon stocks of all other ferralsols (~10 kg C m−2). Here, we investigate processes that allow UF to gain and maintain such extraordinary carbon stocks. Using the International Soil Research and Information Center database, complemented with recently published datasets, we show that the carbon saturation capacity of the clay + silt fractions in UF (22.8 ± 5.7 g C kg−1 soil, n = 59) does not exceed the carbon saturation capacity in other ferralsols (23.3 ± 6.2 g C kg−1 soil, n = 165), thus eliminating a particularly retentive mineral matrix as a possible explanation. Rather, carbon stocks were correlated with the thickness of A horizons (106 ± 49 cm, n = 59 in umbric versus 35 ± 22 cm, n = 165 in non‐umbric ferralsols). We subsequently hypothesized that differences in A‐horizon thickness arose from two pedogenic scenarios: (i) superior carbon accrual resulting from a unique vegetation cover capable of allocating large quantities of carbon to belowground plant organs; and (ii) geomorphic processes that led to carbon burial. We evaluated the plausibility of these scenarios considering landscape history and associated carbon flux rates, hillslope position, as well as δ13C values and Ti/Zr ratios for subsets of ferralsol profiles studied by us in a region that encompasses latitudes from 26 to 7°S in eastern Brazil. We found that exceptional carbon stocks were most prevalent in the gradual transition zone (ecotone) between savanna and rainforest, likely resulting from erosion–deposition processes, historic changes of vegetation cover composed of grasses and arboreal elements, and active bioturbation. We suggest that attempts to sequester carbon in non‐umbric ferralsols will be most successful if they emulate or promote the biotic and abiotic processes prevalent in the savanna/rainforest ecotone.
Treatment modalities, adverse events, and survival outcomes in older patients with head and neck squamous cell carcinoma
Authors: Amr Sania , Ioffe Dina , Suzuki Ikumi , Mehra Ranee , Cullen Kevin , Goloubeva Olga 
Published: October 2021

AbstractBackgroundChemoradiation with curative intent in older adults with locally advanced head and neck squamous cell carcinoma (HNSCC) has been a challenge, because of its potential toxicities.MethodsWe selected primary HNSCC cases from the SEER‐Medicare linked database, assessed overall survival (OS) and adverse events and their associations with different treatments, across four age groups including the youngest (66–69 years) and the oldest (≥80 years).ResultsBetter OS was associated with chemoradiation compared to radiation alone, not only in all patients (N = 5879) (hazard ratio [HR] = 0.82, p < 0.001), but also in the oldest group (N = 1380) (HR = 0.77, p = 0.006) in whom the adverse events rates were not higher than those in the youngest (N = 1562); more of the latter (26%–30%) than the former (14%–19%) received chemoradiation, regardless of their comorbidity indices.ConclusionsOur findings provide evidence that patients' characteristics, other than chronological age, should be equally considered in selecting the best therapy for older patients with HNSCC.
Gut microbiome features associated with liver fibrosis in Hispanics, a population at high risk for fatty liver disease
Authors: Kwan Suet‐Ying , Jiao Jingjing , Joon Aron , Wei Peng , Petty Lauren E. , Below Jennifer E. , Daniel Carrie R. , Wu Xiaogang , Zhang Jianhua , Jenq Robert R. , Futreal P. Andrew , Hawk Ernest T. , McCormick Joseph B. , Fisher‐Hoch Susan P. , Beretta Laura 
Published: October 2021

Abstract

Background and Aims
Hispanics are disproportionately affected by NAFLD, liver fibrosis, cirrhosis, and HCC. Preventive strategies and noninvasive means to identify those in this population at high risk for liver fibrosis, are urgently needed. We aimed to characterize the gut microbiome signatures and related biological functions associated with liver fibrosis in Hispanics and identify environmental and genetic factors affecting them.

Approach and Results
Subjects of the population‐based Cameron County Hispanic Cohort (CCHC; n = 217) were screened by vibration‐controlled transient elastography (FibroScan). Among them, 144 (66.7%) had steatosis and 28 (13.0%) had liver fibrosis. The gut microbiome of subjects with liver fibrosis was enriched with immunogenic commensals (e.g., Prevotella copri, Holdemanella, Clostridiaceae 1) and depleted of Bacteroides caccae, Parabacteroides distasonis, Enterobacter, and Marinifilaceae. The liver fibrosis‐associated metagenome was characterized by changes in the urea cycle, L‐citrulline biosynthesis and creatinine degradation pathways, and altered synthesis of B vitamins and lipoic acid. These metagenomic changes strongly correlated with the depletion of Parabacteroides distasonis and enrichment of Prevotella and Holdemanella. Liver fibrosis was also associated with depletion of bacterial pathways related to L‐fucose biosynthesis. Alcohol consumption, even moderate, was associated with high Prevotella abundance. The single‐nucleotide polymorphisms rs3769502 and rs7573751 in the NCK adaptor protein 2 (NCK2) gene positively associated with high Prevotella abundance.

Conclusion
Hispanics with liver fibrosis display microbiome profiles and associated functional changes that may promote oxidative stress and a proinflammatory environment. These microbiome signatures, together with NCK2 polymorphisms, may have utility in risk modeling and disease prevention in this high‐risk population.
Exposure monitoring toward environmental justice
Authors: Racz LeeAnn , Rish William 
Published: October 2021

Abstract
Executive Order 14008, signed on 27 January 2021, established environmental justice (EJ) as a core priority of the Biden Administration. There is a need for state and federal regulators, as well as industry, to enhance risk assessment methods and exposure monitoring approaches to be more inclusive of EJ community involvement and more representative of EJ community exposures. Cumulative risk assessment models are critical for understanding the unique interaction between chemical exposures and nonchemical stressors that EJ communities encounter daily. Enhanced environmental monitoring with personal and portable sensors, especially when deployed using community partnerships, can capture chemical exposures with sufficient resolution to characterize exposures down to the neighborhood level. Use of internet-linked sensors will also require thoughtful advances in management of big data to inform meaningful and time-sensitive decisions. Integr Environ Assess Manag 2022;18:858–862. © 2021 SETAC
KEY POINTS
There is a need for regulators and industry to enhance risk assessment methods and exposure monitoring approaches to be more inclusive of environmental justice community involvement and more representative of EJ community exposures. Cumulative risk assessment models are critical for understanding the unique interaction between chemical exposures and non-chemical stressors faced by environmental justice communities. Enhanced environmental monitoring with personal and portable sensors, especially when deployed using community partnerships, can capture chemical exposures with sufficient resolution to characterize exposures down to the neighborhood level. Use of internet-linked sensors will also require thoughtful advances in management of big data to inform meaningful and time-sensitive decisions.
Modeling-Based Bone Formation After 2 Months of Romosozumab Treatment: Results From the FRAME Clinical Trial
Authors: Eriksen Erik F , Chapurlat Roland , Boyce Rogely Waite , Shi Yifei , Brown Jacques P , Horlait Stéphane , Betah Donald , Libanati Cesar , Chavassieux Pascale 
Published: October 2021

ABSTRACT
The bone-forming agent romosozumab is a monoclonal antibody that inhibits sclerostin, leading to increased bone formation and decreased resorption. The highest levels of bone formation markers in human patients are observed in the first 2 months of treatment. Histomorphometric analysis of bone biopsies from the phase 3 FRAME trial (NCT01575834) showed an early significant increase in bone formation with concomitant decreased resorption. Preclinical studies demonstrated that most new bone formation after romosozumab treatment was modeling-based bone formation (MBBF). Here we analyzed bone biopsies from FRAME to assess the effect of 2 months of romosozumab versus placebo on the surface extent of MBBF and remodeling-based bone formation (RBBF). In FRAME, postmenopausal women aged ≥55 years with osteoporosis were randomized 1:1 to 210 mg romosozumab or placebo sc every month for 12 months, followed by 60 mg denosumab sc every 6 months for 12 months. Participants in the bone biopsy substudy received quadruple tetracycline labeling and underwent transiliac biopsies at month 2. A total of 29 biopsies were suitable for histomorphometry. Using fluorescence microscopy, bone formation at cancellous, endocortical, and periosteal envelopes was classified based on the appearance of underlying cement lines as modeling (smooth) or remodeling (scalloped). Data were compared using the Wilcoxon rank-sum test, without multiplicity adjustment. After 2 months, the median percentage of MBBF referent to the total bone surface was significantly increased with romosozumab versus placebo on cancellous (18.0% versus 3.8%; p = 0.005) and endocortical (36.7% versus 3.0%; p = 0.001), but not on periosteal (5.0% versus 2.0%; p = 0.37) surfaces, with no significant difference in the surface extent of RBBF on all three bone surfaces. These data show that stimulation of bone formation in the first 2 months of romosozumab treatment in postmenopausal women with osteoporosis is predominately due to increased MBBF on endocortical and cancellous surfaces. © 2021 The Authors. Journal of Bone and Mineral Research published by Wiley Periodicals LLC on behalf of American Society for Bone and Mineral Research (ASBMR).
Abstract
Bone biopsies from the FRAME trial were analyzed to evaluate MBBF and RBBF after romosozumab treatment. After 2 months, the median percentage of MBBF referent to the total bone surface was significantly increased with romosozumab vs placebo on cancellous and endocortical, but not periosteal surfaces, with no significant difference in the surface extent of RBBF on all three bone surfaces. MBBF, modeling-based bone formation; RBBF, remodeling-based bone formation
Clearance of Senescent Cells From Injured Muscle Abrogates Heterotopic Ossification in Mouse Models of Fibrodysplasia Ossificans Progressiva
Authors: Wang Haitao , Zhang Qiang , Kaplan Frederick S. , Pignolo Robert J. 
Published: October 2021

ABSTRACT
Fibrodysplasia ossificans progressiva (FOP) is a rare genetic disease caused by mutations in activin A receptor type I/activin-like kinase 2 (ACVR1/ALK2), a bone morphogenetic protein (BMP) type I receptor, resulting in the formation of extraskeletal or heterotopic ossification (HO) and other features consistent with premature aging. During the first decade of life, episodic bouts of inflammatory swellings (flare-ups) occur, which are typically triggered by soft tissue trauma. Through an endochondral process, these exacerbations ultimately result in skeletal muscles, tendons, ligaments, fascia, and aponeuroses transforming into ectopic bone, rendering movement impossible. We have previously shown that soft tissue injury causes early FOP lesions characterized by cellular hypoxia, cellular damage, and local inflammation. Here we show that muscle injury in FOP also results in senescent cell accumulation, and that senescence promotes tissue reprogramming toward a chondrogenic fate in FOP muscle but not wild-type (WT) muscle. Using a combination of senolytic drugs we show that senescent cell clearance and reduction in the senescence associated secretory phenotype (SASP) ameliorate HO in mouse models of FOP. We conclude that injury-induced senescent cell burden and the SASP contribute to FOP lesion formation and that tissue reprogramming in FOP is mediated by cellular senescence, altering myogenic cell fate toward a chondrogenic cell fate. Furthermore, pharmacological removal of senescent cells abrogates tissue reprogramming and HO formation. Here we provide proof-of-principle evidence for senolytic drugs as a future therapeutic strategy in FOP. © 2021 American Society for Bone and Mineral Research (ASBMR).
An efficient synthesis of 4,6‐diarylnicotinonitrile‐acetamide hybrids via 1,2,3‐triazole linker as multitarget microbial inhibitors
Authors: El‐Sayed Hassan A. , Moustafa Ahmed H. , Masry Asmaa A. , Amer Atef M. , Mohammed Samar M. 
Published: October 2021

AbstractAn efficient and smart approach for design and synthesis of a novel series of nicotinonitrile‐1,2,3‐triazole‐acetamide hybrids was described. The synthetic methodology was commenced with preparation of acetylene derivatives via alkynylation of 2‐oxonicotinonitrile with propargyl bromide under mild basic catalyst (pot. carbonate). The facile click cycloaddition reaction of alkynes 2a‐f and azido‐acetamides 3‐5 in the presence of catalytic Cu(I) in H2O/tetrahydrofuran (THF) was utilized for the synthesis of target molecules 6a‐l. Triazoles 6c, d, f, and 6i have highly activity against the four pathogenic bacteria (Escherichia coli, Pseudomonas aeruginosa, Bacillus subtilis, and Staphylococcus aureus) and two pathogenic fungi (Candida albicans and Aspergillus flavus) with minimum inhibitory concentration (MIC) in between 0.5 and 4 μg/ml for bacteria and 0.5 and 8 μg/ml for fungi.