bluuebunny/crossref_metadata_2025 huggingface dataset:
Opioid Dose Trajectories and Associations With Mortality, Opioid Use Disorder, Continued Opioid Therapy, and Health Plan Disenrollment
Authors: Binswanger Ingrid A. , Shetterly Susan M. , Xu Stanley , Narwaney Komal J. , McClure David L. , Rinehart Deborah J. , Nguyen Anh P. , Glanz Jason M.
Published: October 2022

Importance

Uncertainty remains about the longer-term benefits and harms of different opioid management strategies, such as tapering and dose escalation. For instance, opioid tapering could help patients reduce opioid exposure to prevent opioid use disorder, but patients may also seek care elsewhere and engage in nonprescribed opioid use.

Objective

To evaluate the association between opioid dose trajectories observed in practice and patient outcomes.

Design, Setting, and Participants

This retrospective cohort study was conducted in 3 health systems in Colorado and Wisconsin. The study population included patients receiving long-term opioid therapy between 50 and 200 morphine milligram equivalents between August 1, 2014, and July 31, 2017. Follow-up ended on December 31, 2019. Data were analyzed from January 2020 to August 2022.

Exposures

Group-based trajectory modeling identified 5 dosing trajectories over 1 year: 1 decreasing, 1 high-dose increasing, and 3 stable.

Main Outcomes and Measures

Primary outcomes assessed after the trajectory period were 1-year all-cause mortality, incident opioid use disorder, continued opioid therapy at 1 year, and health plan disenrollment. Associations were tested using Cox proportional hazards regression and log-binomial models, adjusting for baseline covariates.

Results

A total of 3913 patients (mean [SD] age, 59.2 [14.4] years; 2767 White non-Hispanic [70.7%]; 2237 female patients [57.2%]) were included in the study. Compared with stable trajectories, the decreasing dose trajectory was negatively associated with opioid use disorder (adjusted hazard ratio [aHR], 0.40; 95% CI, 0.29-0.55) and continued opioid therapy (site 1: adjusted relative risk [aRR], 0.39; 95% CI, 0.34-0.44), but was positively associated with health plan disenrollment (aHR, 1.66; 95% CI, 1.24-2.22). The decreasing trajectory was not associated with mortality (aHR, 1.28; 95% CI, 0.87-1.86). In contrast, the high-dose increasing trajectory was positively associated with mortality (aHR, 2.19; 95% CI, 1.44-3.32) and opioid use disorder (aHR, 1.81; 95% CI, 1.39-2.37) but was not associated with disenrollment (aHR, 0.90; 95% CI, 0.56-1.42) or continued opioid therapy (site 1: aRR, 0.98; 95% CI, 0.94-1.03).

Conclusions and Relevance

In this cohort study, decreasing opioid dose was associated with reduced risk of opioid use disorder and continued opioid therapy but increased risk of disenrollment compared with stable dosing, whereas the high-dose increasing trajectory was associated with an increased risk of mortality and opioid use disorder. These findings can inform opioid management decision-making.
Patient Use of Physicians’ First (Given) Name in Direct Patient Electronic Messaging
Authors: Harvey Jamison A. , Butterfield Richard J. , Ochoa Shari A. , Yang Yul W.
Published: October 2022

This cohort study examines factors that may contribute to whether patients address physicians differently through electronic messaging
Resource booms, state economic conditions, and child food security
Authors: Cho Seung Jin , Kreider Brent , Winters John V.
Published: October 2022

Child food security is a longstanding concern to policymakers, exacerbated by economic slack and instability. We use the fracking era oil and gas boom of the early 2000s as a natural experiment to examine the importance of state economic conditions for child food security. The fracking boom was a large and unexpected economic shock that substantially improved labor market conditions in states with oil and gas resources but not elsewhere. We find that increases in oil and gas labor income improve child food security, especially for children with less educated parents and those residing in single‐mother households.
Vedolizumab‐related agranulocytosis with Epstein‐Barr virus esophagitis: A case report
Authors: Le Puo‐Hsien , Wu Ren‐Chin , Chen Chien‐Ming , Kuo Chia‐Jung , Su Ming‐Yao , Chiu Cheng‐Tang
Published: October 2022

Vedolizumab has a good safety profile for the treatment of inflammatory bowel disease. Agranulocytosis is a rare but fatal condition. Although many drugs are considered to have a high risk of agranulocytosis, no previous study has mentioned vedolizumab. A 71‐year‐old female with Sjogren's syndrome received vedolizumab treatment for moderate to severe ulcerative colitis. Her symptoms improved; however, leukopenia was noted after the first dose. Four days after the second dose, she complained of oral and chest pain. Agranulocytosis, oral candidiasis, and Epstein‐Barr virus esophagitis with ulceration were noted. After granulocyte‐colony stimulating factor treatment, the white blood cell count returned to normal and the esophageal ulcers healed. Vedolizumab is a very safe gut‐selective biologic agent, but it also carries the risk of agranulocytosis.
Role of serum‐free light chain assay for defining response and progression in immunoglobulin secretory multiple myeloma
Authors: Tacchetti Paola , Rocchi Serena , Zamagni Elena , Barbato Simona , Rizzello Ilaria , De Cicco Gabriella , Pantani Lucia , Mancuso Katia , Fusco Alessio , Dozza Luca , Ursi Margherita , Favero Emanuele , Terragna Carolina , Testoni Nicoletta , Cavo Michele
Published: October 2022

The International Myeloma Working Group (IMWG) guidelines recommend using electrophoresis and immunofixation to define response and progressive disease (PD) in immunoglobulin (Ig) secretory multiple myeloma (Ig‐MM), whereas the role of serum‐free light chain (sFLC) is controversial. We retrospectively analyzed the value of adding sFLC assays in the definition of response and PD according to IMWG criteria in 339 Ig‐MM patients treated with a first‐line novel agent‐based therapy (median follow‐up 54 months). sFLC PD was defined according to conventional criteria plus increased sFLC levels, or sFLC escape (sFLCe); progression/sFLCe‐free survival (ePFS) was the time from the start of treatment to the date of first PD or sFLCe, or death; overall survival after PD/sFLCe (OS after Pe) was the time from first PD or sFLCe to the date of death. 148 (44%) patients achieved a complete response and 198 (60%) a normal sFLC ratio (sFLCR). sFLCR normalization was an independent prognostic factor for extended PFS (HR = 0.46, p = 0.001) and OS (HR = 0.47, p = 0.006) by multivariable analysis. 175 (52%) patients experienced PD according to the IMWG criteria, whereas 180 (53%) experienced PD or sFLCe. Overall, a sFLCe was observed in 31 (9%) patients. Median PFS and ePFS were both equal to 36 (95% CI = 32–42, and 32–40, respectively) months. sFLC PD adversely affected the OS after Pe compared to PD with increasing monoclonal Ig only (HR = 0.52, p = 0.012). Our results support the inclusion of the sFLC assay for defining response and PD in Ig‐MM.
Nachhaltiges Design von Struktur‐ und Funktionspolymeren für die Kreislaufwirtschaft
Authors: von Vacano Bernhard , Mangold Hannah , Vandermeulen Guido W. M. , Battagliarin Glauco , Hofmann Maximilian , Bean Jessica , Künkel Andreas
Published: October 2022

Für eine nachhaltige Kreislaufwirtschaft müssen Polymere auf rezyklierte und biobasierte Rohstoffe umgestellt werden, und sie müssen bezüglich der Emissionen CO2‐neutral werden. Dies gilt nicht nur für Strukturpolymere, z. B. in Verpackungen oder technischen Anwendungen, sondern auch für Funktionspolymere in flüssigen Formulierungen: in Klebstoffen oder Schmiermitteln, als Verdickungs‐ oder Dispersionsmittel. Am Ende ihrer Lebensdauer müssen Polymere entweder gesammelt und technisch rezykliert werden oder biologisch abbaubar sein, wenn sie nicht sammelbar sind. Fortschritte in der Polymerchemie, in Anwendungen und durch zunehmend rechnergestützte Methoden der Materialwissenschaft ermöglichen einen ganzheitlichen Ansatz: Polymere werden bereits für ihre Rezyklierbarkeit oder biologische Abbaubarkeit konzipiert. Dieser Aufsatz zeigt, wie neue wissenschaftliche Erkenntnisse in Verbindung mit entsprechenden rechtlichen, gesellschaftlichen und wirtschaftlichen Randbedingungen den Weg zu einer umfassenden Kreislaufwirtschaft für Polymere weisen können.
Biosynthetic Elucidation and Structural Revision of Brevione E: Characterization of the Key Dioxygenase for Pathway Branching from Setosusin Biosynthesis
Authors: Yan Dexiu , Matsuda Yudai
Published: October 2022

Brevione E (1) is a fungal hexacyclic meroditerpenoid with unique oxepane and cycloheptenone moieties. In this study, we identified the biosynthetic gene cluster of 1 and elucidated its biosynthetic pathway via heterologous expression of the biosynthetic genes and in vitro enzymatic reactions. Surprisingly, reexamination of the structure of 1 revealed a substituted tetrahydrofuran ring instead of the previously proposed oxepane system. Moreover, we determined that cycloheptenone synthesis involves skeletal rearrangement catalyzed by the α‐ketoglutarate‐dependent dioxygenase BrvJ. BrvJ is highly homologous to SetK, which engages in the biosynthesis of another fungal metabolite, setosusin, and accepts the same substrate as BrvJ but performs only simple hydroxylation. Finally, we identified the key amino acid residues critical for product selectivity of BrvJ and SetK, providing insight into how the biosynthesis pathways of 1 and setosusin diverge and how fungi diversify natural products.
Removal and Degradation of Microplastics Using the Magnetic and Nanozyme Activities of Bare Iron Oxide Nanoaggregates
Authors: Zandieh Mohamad , Liu Juewen
Published: October 2022

Removal and degradation of microplastics are often carried out separately. In this work, hydrophilic bare Fe3O4 nanoaggregates allowed efficient removal of the most common microplastics including high‐density polyethylene, polypropylene, polyvinyl chloride, polystyrene, and polyethylene terephthalate. Full extraction was achieved using Fe3O4 at 1 % of the mass of microplastics. Hydrogen bonding is the main force for the adsorption of Fe3O4. Unlike the more commonly used hydrophobically modified Fe3O4 nanoparticles, the bare Fe3O4 benefitted from the peroxidase‐like activity of its exposed surface, enabling further catalytic degradation of microplastics with nearly 100 % efficiency and easy recovery of the Fe3O4.
Remote Editing of Stacked Aromatic Assemblies for Heteroannular C−H Functionalization by a Palladium Switch between Aromatic Rings
Authors: Yu Zhiqian , Liu Qianhui , Li Qian , Huang Zhenmei , Yang Yudong , You Jingsong
Published: October 2022

An approach allowing remote editing of stacked aromatic assemblies for heteroannular C−H functionalization would represent a transformative chemical toolbox that may make the diversification of complex molecules in a straightforward manner. However, such a C−H activation is usually less kinetically and thermodynamically favorable than homoannular ortho C−H activation and remains a fundamental challenge. Herein we disclose an engineer's approach, using a transient ligand as an interim bridge between two aryl rings (analogues to mountaintops) to anchor the metal center on the remote heteroannular C−H bond. As a proof‐of‐concept, we present the palladium‐catalyzed heteroannular C−H olefination of stacked aromatic assemblies with olefins and allylation with vinyl acetates using L‐tert‐leucine acid as a transient ligand. Mechanistic investigations suggest an unusual olefin coordination‐promoted interannular palladium migration process determinative for reversal of the site‐selectivity.
Synthesis of Axially Chiral Biaryls via Enantioselective Ullmann Coupling ofortho‐Chlorinated Aryl Aldehydes Enabled by a Chiral 2,2′‐Bipyridine Ligand
Authors: Perveen Saima , Zhang Shuai , Wang Linghua , Song Peidong , Ouyang Yizhao , Jiao Jiao , Duan Xin‐Hua , Li Pengfei
Published: October 2022

The first nickel‐catalyzed highly enantioselective reductive Ullmann coupling ofortho‐chlorinated aryl aldehyde was achieved under mild reaction conditions with a chiral 2,2′‐bipyridine ligand (+)‐DTB‐SBpy, thus providing axially chiral biphenyl or binaphthyl dials with up to 99 % yield and 99.5:0.5 er. The versatility of the products as common synthetic intermediates for diverse axially chiral ligands, catalysts, and functional molecules was demonstrated by short‐step transformations. This protocol also allowed the concise and highly enantioselective formal total synthesis of biologically active natural products (+)‐kotanin, (−)‐isoschizandrin and (+)‐gossypol.
Copper‐Catalyzed Carboxylation of Aryl Thianthrenium Salts with CO2
Authors: Tang Shibiao , Zhao Xiaobo , Yang Lidong , Li Bin , Wang Baiquan
Published: October 2022

Carboxyl group is one of the most widely used groups in organic synthesis. Herein, an efficient copper‐catalyzed carboxylation of aryl thianthrenium salts with carbon dioxide (CO2) at room temperature has been developed. The reaction employs low loading of cuprous chloride catalyst under 1 atm CO2 and exhibits good functional group tolerance. In combination with C−H thianthrenation of aromatic hydrocarbons, this work provides an efficient method for the site‐selective C−H carboxylation of aromatic hydrocarbons. It may serve as a significant late‐stage carboxylation tool for the modification of drug molecules in the future.
Hydrogen‐Bonded Organic Framework for High‐Performance Lithium/Sodium‐Iodine Organic Batteries
Authors: Guo Chaofei. , Han Bo , Sun Weiwei. , Cao Yingnan. , Zhang Yifan. , Wang Yong
Published: October 2022

The rechargeable lithium/sodium‐iodine battery (Li/Na‐I2) is a promising candidate for meeting the growing energy demand. Herein, a flexible hydrogen‐bonded organic framework (HOF) linked to the Ti3C2TxMXene complex (HOF@Ti3C2Tx) has been presented for iodine loading. HOF is self‐assembled by organic monomers through hydrogen bonding interactions between each monomer. It leads to numerous cavities in HOF structure, which can encapsulate iodine through various adsorptive sites and intermolecular interactions. The unique structure of complex can accelerate the nucleation of iodine, achieve fast reaction kinetics, stabilize iodide and retard the shuttle effect, thus improving the cycling stability of I2‐based batteries. The I2/HOF@Ti3C2Txexhibits large reversible capacities of 260.2 and 207.6 mAh g−1at 0.2 C after repeated cycling for Li‐I2and Na‐I2batteries, respectively. This work can gain insights into the HOF‐related energy storage application with reversible iodine encapsulation and its related redox reaction mechanisms with Li and Na metal ions.
Hewettite ZnV6O16 ⋅ 8H2O with Remarkably Stable Layers and Ultralarge Interlayer Spacing for High‐Performance Aqueous Zn‐Ion Batteries
Authors: Zhu Kaiyue , Jiang Weikang , Wang Zhengsen , Li Weijian , Xie Weili , Yang Hanmiao , Yang Weishen
Published: October 2022

Aqueous Zn‐ion batteries (ZIBs) are promising candidates for grid‐scale energy storage because of their intrinsic safety, low‐cost and high energy‐intensity. Vanadium‐based materials are widely used as the cathode of ZIBs, especially A2V6O16 ⋅ nH2O (AVO, A=NH4+, Na, K). However, AVO suffers from serious dissolution, phase transformation and narrow gallery spacing (∼3 Å), leading to poor cycling stability and rate capability. Herein, we unveiled the root cause of the performance degradation in the AVO cathode and therefore developed a new high‐performance cathode of ZnV6O16 ⋅ 8H2O (ZVO) for ZIB. Through a method of ion exchange induced phase transformation, AVO was converted to hewettite ZVO with larger gallery spacing (∼6 Å) and more stable V6O16 layers. ZVO cathode thus constructed delivers a high capacity of 365 and 170 mAh g−1 at 0.5 and 15 A g−1, while 86 % and 70 % of its capacity are retained at 0.5 A g−1 after 300 cycles and at 15 A g−1 after 10000 cycles, substantially better than conventional AVO.
pH Dependence of Amyloid‐β Fibril Assembly Kinetics: Unravelling the Microscopic Molecular Processes
Authors: Tian Yao , Viles John H.
Published: October 2022

Central to Alzheimer's disease (AD) is the assembly of the amyloid‐beta peptide (Aβ) into fibrils. A reduction in pH accompanying inflammation or subcellular compartments, may accelerate fibril formation as the pH approaches Aβ’s isoelectric point (pI). Using global fitting of fibril formation kinetics over a range of pHs, we identify the impact net charge has on individual fibril assembly microscopic rate constants. We show that the primary nucleation has a strong pH dependence. The titration behaviour exhibits a mid‐point or pKa of 7.0, close to the pKa of Aβ histidine imidazoles. Surprisingly, both the secondary nucleation and elongation rate constants are pH independent. This indicates the charge of Aβ, in particular histidine protonation, has little impact on this stage of Aβ assembly. These fundamental processes are key to understanding the forces that drive the assembly of Aβ into toxic oligomers and fibrils.
Cross β Amyloid Nanotubes Demonstrate Promiscuous Catalysis in a Chemical Reaction Network via Co‐option
Authors: Roy Soumili , Chatterjee Ayan , Bal Subhajit , Das Dibyendu
Published: October 2022

In Darwin's warm pond rich with nutrients, lesser number of early catalytic machineries with modest capabilities were able to demonstrate promiscuity by catalyzing diverse biochemical transformations important for protometabolism. Herein, we report catalytically promiscuous amyloid‐based short peptide assemblies that could concomitantly catalyse three metabolically important yet orthogonal reactions. The surface exposed catalytic dyads featuring lysines and imidazoles were utilized for C=N condensation via dynamic covalent linkages and modulation of protonation events, respectively. Further, the peptide assemblies could promiscuously catalyse hydrolysis as well as retro‐aldol reactions, that could be co‐opted to facilitate C=N bond formation, either by a feedforward‐driven reaction network or by replenishing depleted substrates. The catalytic diversity of short peptide based promiscuous β‐sheet folds suggests their possible role in promoting the protometabolic network in early earth.
Synchronizing Two Distinct Nano‐Circular Sliding Motions in Six‐Component Machinery for Double Catalysis
Authors: Rajasekaran Vishnu Verman , Ghosh Amit , Kundu Sohom , Mondal Debabrata , Paululat Thomas , Schmittel Michael
Published: October 2022

The heteroleptic multi‐component double slider‐on‐deck systemDS3exhibits tight coupling of motional speed of two distinct nano‐circular sliders (k298=77 and 41 kHz) despite a 2.2 nm separation. In comparison, the single sliders inDS1andDS2move at vastly different speed (k298=1.1 vs. 350 kHz). Synchronization of the motions inDS3remains even when one slows the movement of the faster slider using small molecular brake pads. In contrast to the individualDS1andDS2systems,DS3is a powerful catalyst for a two‐step reaction by using the motion of both sliders to drive two catalytic processes.
3D‐printing polylactic acid/hydroxyapatite fracture internal fixation plates for bone repair
Authors: Xia Yuhao , Xu Wei , Zhang Hongbiao , Wu Xiaopei , Dai Honglian
Published: October 2022

Fracture internal fixation plates are the most common implants in internal fixation and have been applied to fix fractures for over a hundred years. Plates of metal material remain the gold standard. However, they are not the ideal bone plate considering the stress shielding induced by the high elastic modulus and biomechanical mismatch with bone. PLA fracture internal fixation plates present the advantages of matching with the elastic modulus of the bone and absorbable properties but are limited by poor toughness and acidic degradation. Degradable bone plates composed of polylactic acid/hydroxyapatite (PLA/HA) composite were prepared by fused deposition modeling, which had higher bending strength and compressive strength than that of pure PLA. The hydrophilicity of PLA/HA composite was improved by the addition of HA, it was beneficial to the adhesion of cells on the surface of the composite. The results of in vitro degradability showed that the addition of HA can effectively neutralize the acidity generated by PLA degradation. Meanwhile, the addition of HA can improve the cell affinity to promote the adhesion and growth of MC3T3‐E1 cells on the surface of the composites. Consequently, the PLA/HA composite shows a good potential as a bone plate to fix bone fractures.
Evaluation of bleeding and anticoagulation markers by edoxaban and low‐dose cyclosporine: A case series study
Authors: Hirai Toshinori , Shinogi Yuri , Ikejiri Makoto , Murata Tomohiro , Iwamoto Takuya
Published: October 2022

It was reported that high‐dose cyclosporine at 500 mg daily increases edoxaban exposure. We investigated whether cyclosporine <500 mg daily leads to edoxaban‐induced bleeding in the clinical setting. This case series study included patients receiving edoxaban and cyclosporine at Mie University Hospital. The outcomes were bleeding and anticoagulant markers, including activated partial thromboplastin time (APTT), prothrombin time (PT), and the international normalized ratio of prothrombin time (PT‐INR). We examined the genotypes of cytochrome P450 3A5 (CYP3A5), multidrug resistance 1 (ABCB1), and solute carrier organic anion transporter 1B1 (SLCO1B1). Trends in anticoagulant markers were analyzed. Thirteen patients received edoxaban (standard dose; n = 3 and reduced dose; n = 10) and cyclosporine (1.94 ± 1.42 mg/kg). A bleeding event occurred in one patient receiving a standard dose of edoxaban plus cyclosporine of 25 mg daily (HAS‐BLED score of 2 and genotypes; CYP3A5*3/*3, ABCB1 3435CT, and SLCO1B1*1a/*1b). After edoxaban treatment, anticoagulant markers were prolonged (APTT; 27.95 ± 3.64 s vs. 31.11 ± 3.90 s, p < 0.001, PT; 11.53 ± 1.01 s vs. 13.03 ± 0.98 s, p = 0.002, PT‐INR; 0.98 ± 0.09 vs. 1.11 ± 0.11, p = 0.007). In summary, the genotypes of CYP3A5, ABCB1, and SLCO1B1 and the dosage of edoxaban may affect the risk of bleeding by edoxaban when co‐administered with cyclosporine, even at low doses.
“We are better and happier if we are inclusive.” Therapist perspectives on the importance of LGB cultural competence in a mental health setting
Authors: Bishop Joshua , Crisp Dimity , Scholz Brett
Published: October 2022

Lesbian, gay and bisexual people are more likely than their heterosexual counterparts to report dissatisfaction after accessing a counselling or psychological service. Greater dissatisfaction may result from therapists who focus on psychopathology without considering cultural context. Research has demonstrated therapists' cultural competence (attitudes, knowledge and skills) may influence effective service provision to LGB people. Counsellors and psychologists (N = 10) were interviewed to determine the sources of information influencing the cultural competence and LGB cultural competence practices used by therapists in their clinical practice. Three themes were developed from semistructured interviews: (1) the importance of multiple sources of cultural competence; (2) applying cultural competence improves the therapeutic process; and (3) ensuring visual cues of affirmation are affirming, not pathologising. Theme 1 highlighted that initial professional training, cultural competence training and lived experience could be triangulated to assist therapists in improving their cultural competence. Theme 2 highlighted that cultural competence improves the therapeutic process by ensuring therapists can demonstrate affirming attitudes, knowledge about LGB people and culturally affirming skills to work effectively with LGB clients. The final theme explored the need for therapists to create an inclusive space for LGB clients. Recommendations for improving clinical practices and tools to enhance cultural competence are discussed.
Phytochemicals and Biological Activities of Burdock (Arctium lappa L.) Extracts: A Review
Authors: de Souza Ariádine Reder Custodio , de Oliveira Thais Latansio , Fontana Pâmela Dias , Carneiro Milena Carvalho , Corazza Marcos Lúcio , de Messias Reason Iara Jose , Bavia Lorena
Published: October 2022

Arctium lappa L., also known as burdock, is an edible wild plant which has the ability to grow in distinct environments and is considered a weed in several parts of the world. This species has great value in the biological and medical fields with its major secondary components being phenolic compounds and terpenes, substances rich in desired biological activities as antioxidant, antimicrobial, antitumor and anti‐inflammatory. In addition, burdock leaves extracts have shown a modulatory effect on the complement system, which plays an important role in the development of inflammatory diseases, with an inhibitory effect on all complement pathways. Thus, natural products with those relevant activities are promising agents for healthcare applications. Therefore, the species A. lappa may represent an interesting asset for researching and developing new therapies for inflammatory afflictions.
Optogenetic Protein Cleavage in Zebrafish Embryos**
Authors: Brown Wes , Albright Savannah , Tsang Michael , Deiters Alexander
Published: October 2022

A wide array of optogenetic tools are available that allow for precise spatiotemporal control over cellular processes. These tools are particularly important to zebrafish researchers who take advantage of the embryo's transparency. However, photocleavable optogenetic proteins have not been utilized in zebrafish. We demonstrate successful optical control of protein cleavage in embryos using PhoCl, a photocleavable fluorescent protein. This optogenetic tool offers temporal and spatial control over protein cleavage events, which we demonstrate in light‐triggered protein translocation and light‐triggered apoptosis.
Improved Corrosion‐Resistance and Regulated Electro‐state of Elastic Polyaniline Coated Nickel Phosphide for Efficient Water Oxidation
Authors: Zhu Zhiwei , Zhang Yadong , Wang Hong , Xia Bao Yu , You Bo
Published: October 2022

Electrocatalysis is at the heart of energy conversion in sustainable energy systems, during which the involved electrocatalysts usually undergo dynamic reconstruction. Such reconstruction normally leads to structure corrosion and collapse which lower the electrochemically active surface area, blocks the diaphragm and increases the internal resistance of the electrolyzer, collectively resulting in inferior energy conversion efficiency. Herein, we report an efficient polyaniline (PANi) confining strategy to address the above issues using Ni5P4 for the oxygen evolution reaction (OER) as an example. Experiments and DFT computations reveal that the elastic PANi can adaptively buffer the structure corrosion of Ni5P4 during oxidative reconstruction and positively charge the reconstruction‐formed nickel (oxy)(hydr)oxides for optimal binding of OER intermediates, jointly leading to significantly improved performance featuring a long‐term stability at 100 mA cm−2 with a low overpotential of only 280 mV. This facile strategy can be effectively extendable to other compound catalysts in electrocatalytic reactions.
Merging Rh‐Catalyzed C‐H Functionalization and Cascade Cyclization to Enable Propargylic Alcohols as Three‐Carbon Synthons**
Authors: Nagtilak Prajyot Jayadev , Mane Manoj V. , Prasad Supreeth , Cavallo Luigi , Tantillo Dean J. , Kapur Manmohan
Published: October 2022

Reported herein is a reactivity of propargyl alcohols as “Three‐Carbon Synthons” in a Rh(III)‐catalyzed C−H functionalization of acetanilides, leading to the synthesis of core structures of isocryptolepine, γ‐carbolines, dihydrochromeno[2,3‐b]indoles, and diindolylmethanes (DIM) derivatives. The transformation involves a rhodium(III)‐catalyzed C−H functionalization and heteroannulation to yield indoles followed by a cascade cyclization with both external and internal nucleophiles to afford diverse products. The role of the hydroxy group, the key function of the silver additive, the origin of the reverse regioselectivity and the rate‐determining step, are rationalized in conformity with the combination of experimental, noncovalent interaction analysis and DFT studies. This protocol is endowed with several salient features, including one‐pot multistep cascade approach, exclusive regioselectivity, good functional group tolerance and synthesis of variety of molecular frameworks.
Theoretical Exploitation of 1,2,3,4,5,6‐Hexachloro‐ and 1,2,3,4,5,6‐Hexafluorocyclohexane Isomers as Biologically Active Compounds
Authors: Martins Francisco A. , Freitas Matheus P.
Published: October 2022

Hexachlorocyclohexanes (HCHs) have been widely explored as biological compounds during the last century. However, most of them were banned due to their potential toxicity in humans, animals, and the environment. Revisiting HCHs to explore their biological activity while improving key features is valuable and may lead to a new class of pesticides that utilizes the biological response of HCHs without their toxic characteristics. In this sense, the fluorine atom can be a possible alternative since a large number of therapeutics and agrochemicals have been developed with this halogen in their structure. We have evaluated herein the conformational behavior of HCHs and their bioisosteric fluorinated compounds, namely, hexafluorocyclohexanes (HFHs), through quantum‐chemical calculations. We also explored the potential of the HCH and HFH isomers as biological compounds by docking them inside three possible targets. It was demonstrated that HCH and HFH have similar ligand‐protein interactions with three pockets: the picrotoxin and barbiturate sites of the GABAA receptor and the ryanodine receptor. The results support HFHs as possible alternatives for HCHs since the replacement of Cl with F does not forfeit the main ligand‐protein interactions. Finally, we demonstrated that HFHs have a lower log P than HCHs by almost two logarithmic units. This result highlights the role of fluorine in distribution and bioaccumulation.
Low‐Cost and Scalable Ni‐Prussian Blue Analogue//Functionalized Carbon Based Na‐Ion Systems for all Climate Operations
Authors: Naskar Pappu , Debnath Subhrajyoti , Maiti Apurba , Biswas Biplab , Banerjee Anjan
Published: October 2022

Herein, we have developed a sodium ion based aqueous energy storage device with nickel prussian‐blue‐analogue (Ni‐PBA) positive and functionalized carbon‐black negative electrodes in 1 M Na2SO4 electrolyte solution. The components required to develop the device, i. e., stainless steel (SS) current‐collectors, absorbent‐glass‐mat separator, electrolyte, carbon‐black, and precursors of Ni‐PBA, are all environmentally benign and inexpensive. To minimize the corrosion of pristine‐SS, polyaniline coating on the SS surface is applied by in situ electrodeposition method. The full cell exhibits a specific capacity of 28 mAh g−1 with 90 % Coulomb efficiency (@0.2C), an energy density of 34 Wh kg−1 (@20 W kg−1), a power density of 100 W kg−1 (@18 Wh kg−1) and a good life cycle (70 % capacity‐retention over 500 cycles @1.0C rate) within the 0–1.2 V window. The cell performance is further tested under variable temperatures, and 0–50 °C range is reported to be the working window for this cell.
Unifying the Nitrogen Reduction Activity of Anatase and Rutile TiO2 Surfaces
Authors: Ji Yongfei , Liu Paiyong , Fan Ting
Published: October 2022

TiO2 is a model transition metal oxide that has been applied frequently in both photocatalytic and electrocatalytic nitrogen reduction reactions (NRR). However, the phase which is more NRR active still remains a puzzle. This work presents a theoretical study on the NRR activity of the (001), (100), (101), and (110) surfaces of both anatase and rutile TiO2. We found that perfect surfaces are not active for NRR, while the oxygen vacancy can promote the reaction by providing excess electrons and low‐coordinated Ti atoms that enhance the binding of the key intermediate (HNN*). The NRR activity of the eight facets can be unified into a single scaling line. The anatase TiO2(101) and rutile TiO2(101) surfaces were found to be the most and the second most active surfaces with a limiting potential of −0.91 V and −0.95 V respectively, suggesting that the TiO2 NRR activity is not very phase‐sensitive. For photocatalytic NRR, the results suggest that the anatase TiO2(101) surface is still the most active facet. We further found that the binding strength of key intermediates scale well with the formation energy of oxygen vacancy, which is determined by the oxygen coordination number and the degree of relaxation of the surface after the creation of oxygen vacancy. This work provides a comprehensive understanding of the activity of TiO2 surfaces. The results should be helpful for the design of more efficient TiO2‐based NRR catalysts.
Corporate biodiversity management and organisational change mechanisms: The case of a tea producer in Sri Lanka
Authors: Atupola Upekha , Vola Paola , Gunarathne Nuwan , Truant Elisa , Gelmini Lorenzo
Published: October 2022

Corporate biodiversity management (CBDM) is a primary environmental concern in the food and beverage industry, especially the tea sector. However, the way tea‐producing companies pursue sustainable biodiversity management practices, and how these practices lead to organisational change at the lower tiers of the food supply chain remain under‐researched. Using alternative models of organisational change and data from interviews, field visits, and documents, this study analyses the practices adopted by a tea producer in a highly environmentally sensitive area in Sri Lanka, and how these practices have led to organisational change. The findings show that environmental disturbances in the tea industry's value chain primarily influence the organisation's design archetypes, in turn leading to CBDM through organisational subsystems and interpretive schemes. The study shows that adopting CBDM practices gradually and consistently leads to sustainable outcomes over time.
Clonal functional traits favor the invasive success of alien plants into native communities
Authors: Wang Yong‐Jian , Liu Yuan‐Yuan , Chen Duo , Du Dao‐Lin , Müller‐Schärer Heinz , Yu Fei‐Hai
Published: October 2022

Functional traits are frequently proposed to determine the invasiveness of alien species. However, few empirical studies have directly manipulated functional traits and tested their importance in the invasion success of alien species into native plant communities, particularly under global change. We manipulated clonal integration (a key clonal functional trait) of four alien clonal plants by severing inter‐ramet connections or keeping them intact and simulated their invasion into native plant communities with two levels of species diversity, population density and nutrient availability. High community diversity and density impeded the invasion success of the alien clonal plants. Clonal integration of the alien plants promoted their invasion success, particularly in the low‐density communities associated with low species diversity or nutrient addition, which resulted in a negative correlation between the performance of alien plants and native communities, as expected under global change. Thus, clonal integration can favor the invasion success of alien clonal plants into degraded resident communities with a high degree of disturbance and eutrophication. Our findings confirm the role of clonal functional traits in facilitating alien plant invasions into native plant communities and suggest that clonal functional traits should be considered to efficiently restore degraded communities heavily invaded by alien clonal plants.
Electrochemical Realization of 3D Interconnected MoS3/PPy Nanowire Frameworks as Sulfur‐Equivalent Cathode Materials for Li‐S Batteries
Authors: Yu Hongtao , Siebert Andreas , Mei Shilin , Garcia‐Diez Raul , Félix Roberto , Quan Ting , Xu Yaolin , Frisch Johannes , Wilks Regan G. , Bär Marcus , Pei Chun , Lu Yan
Published: October 2022

The development of freestanding and binder‐free electrode is an effective approach to perform the inherent capacity of active materials and promote the mechanism study by minimizing the interference from additives. Herein, we construct a freestanding cathode composed of MoS3/PPy nanowires (NWs) deposited on porous nickel foam (NF) (MoS3/PPy/NF) through electrochemical methods, which can work efficiently as sulfur‐equivalent cathode material for Li‐S batteries. The structural stability of the MoS3/PPy/NF cathode is greatly enhanced due to its significant tolerance to the volume expansion of MoS3 during the lithiation process, which we ascribe to the flexible 3D framework of PPy NWs, leading to superior cycling performance compared to the bulk‐MoS3/NF reference. Eliminating the interference of binder and carbon additives, the evolution of the chemical and electronic structure of Mo and S species during the discharge/charge was studied by X‐ray absorption near‐edge spectroscopy (XANES). The formation of lithium polysulfides was excluded as the driving cathode reaction mechanism, suggesting the great potential of MoS3 as a promising sulfur‐equivalent cathode material to evade the shuttle effect for Li‐S batteries. The present study successfully demonstrates the importance of structural design of freestanding electrode enhancing the cycling performances and revealing the corresponding mechanisms.
Risk of death associated with incident heart failure in patients with known or suspected chronic coronary syndrome
Authors: Núñez Julio , Lorenzo Miguel , Miñana Gema , Palau Patricia , Monmeneu Jose V. , López‐Lereu Maria P. , Gavara Jose , Marcos‐Garcés Víctor , Rios‐Navarro Cesar , Pérez Nerea , de Dios Elena , Núñez Eduardo , Sanchis Juan , Chorro Francisco J. , Bayés‐Genís Antoni , Bodí Vicent
Published: October 2022

Aims

Traditional adverse events in chronic coronary syndrome (CCS) include atherothrombotic events but usually exclude heart failure (HF). Data are scarce about how new‐onset HF modifies mortality risk. We aimed to determine the incidence of HF and compare its long‐term mortality risk with myocardial infarction (MI) and stroke in patients with known or suspected CCS.

Methods

We prospectively evaluated 5811 consecutive HF‐free patients submitted to vasodilator stress cardiac magnetic resonance (CMR) for known or suspected CCS. Ischaemic burden and left ventricular ejection fraction were assessed by CMR. HF included outpatient diagnosis or acute HF hospitalization. The mortality risk for the incident events and their cross‐comparisons were evaluated using a Markov illness–death model with transition‐specific survival models.

Results

The mean age was 55 ± 11 years, and 38.9% were female. At a median follow‐up of 5.44 (IQR = 2.53–8.55) years, 591 deaths were registered (1.79 per 100 P‐Y). The rates of new‐onset HF were higher compared with MI and stroke [1.02, 0.62, and 0.51, respectively (P < 0.05)]. The adjusted association between new‐onset HF, MI, and stroke, and subsequent mortality was time dependent. The risk increased almost linearly for HF and became significant by the third year. By Year 10, the mortality risk attributable to new‐onset HF was more than 2.5‐fold (HR: 2.68, 95% CI = 1.74–4.12). For MI, there was a significant increase in mortality risk up to the second year, followed by a monotonic decrease. For stroke, the mortality risk increased for the entire follow‐up but became significant by the third year. A cross‐comparison among incident endpoints HF outnumbers risk for those with MI by the sixth year (HRyear6.3: 1.88, 95% CI = 1.03–3.43). There was no difference in mortality risk between incident HF and stroke.

Conclusions

In patients with CCS, long‐term rates of incident HF were higher than MI and stroke. Patients with new‐onset HF showed a higher risk of long‐term mortality.
Chalcohalides: A Rising Type of Second‐Order Nonlinear Optical Materials
Authors: Li Jun , Han Shan‐Shan , Guo Sheng‐Ping
Published: October 2022

In the past few decades, many new infrared (IR) second‐order nonlinear optical (NLO) materials have been prepared by various synthetic methods to satisfy the growing market demand. However, few ones have the high potentials to be applicable since their comprehensive NLO properties cannot meet the standards, which include a series of indicators like large NLO effects, high laser‐induced damage thresholds (LIDTs), phase matchability, high thermal stability, good growth habit, and so on. Considering the available IR NLO materials’ disadvantages and the market requirements, it is necessary to continuously explore new high‐performance ones. Hitherto, lots of chalcogenides, halides, and oxides have been explored as IR NLO materials. Recently, researchers have found that the combination of two or more structural units into one structure may achieve good NLO properties, as evidenced by the fact that diverse materials with multiple anions are receiving growing interest. Specifically, chalcohalides are highly promising as they may combine the advantages of chalcogenides and halides,viz. large NLO coefficients and wide IR transparency of the former, and large band gaps and high LIDTs of the latter. To address the status of chalcohalides, this review focuses on the newest progresses on this topic (mainly from the last five years), including ternary chalcohalides, quaternary chalcohalides, salt‐inclusion chalcohalides, and rare‐earth chalcohalides. Here we summarize and analyze their compositions, crystal structures, NLO properties, and discuss the structure‐property relationship. Finally, the development prospects for NLO chalcohalides are given.
Post‐Modification of Amino Acids and Peptides for the Rapid Synthesis of C‐Glycoamino Acids and C‐Glycopeptides
Authors: Yuan Zhenbo , Zhu Changtong , Zhang Yan , Rao Yijian
Published: October 2022

Glycoamino acids and glycoproteins, especially C‐glycoamino acids and C‐glycoproteins, attract tremendous interests in the realm of biology and chemistry due to their wide occurrence in natural products, excellent pharmacodynamic properties and dynamic stability. Compared with the traditional construction of the amino acid or the glycosyl moiety de novo, post‐modification of amino acids and peptides through direct glycosylation reactions constitute a powerful synthetic approach to attaining C‐glycoamino acids and C‐glycopeptides rapidly on account of the high step‐economy, broad functional group tolerance, and conservation of the chirality of the amino acid and glycosyl moieties. In this review, the recent developments in the synthesis of C‐glycoamino acids and C‐glycopeptides via the post‐modification of amino acids and peptides are summarized. Additionally, the important and representative examples, synthetic applications, and crucial mechanism investigations of these glycosylation reactions are also highlighted.
Virtual reality hypnosis in the management of pain: Self‐reported and neurophysiological measures in healthy subjects
Authors: Rousseaux Floriane , Panda Rajanikant , Toussaint Clémence , Bicego Aminata , Niimi Masachika , Faymonville Marie‐Elisabeth , Nyssen Anne‐Sophie , Laureys Steven , Gosseries Olivia , Vanhaudenhuyse Audrey
Published: October 2022

Background

Virtual reality hypnosis (VRH) has emerged as a new and promising option for pain management. Nonetheless, neural dynamics of pain modulation during VRH have not been investigated yet. The aim of this study was to measure the effects of VRH on pain, combining neurophysiological and self‐reported measurements.

Methods

Eighteen healthy subjects underwent noxious electrical stimulations in both normal wakefulness and VRH conditions. Dissociation, absorption, time perception, anxiety, pain intensity and unpleasantness, heart rate variability and breathing were reported for each condition. EEG signals were analysed using event‐related potentials (ERP) and time–frequency response (TFR) time‐locked to stimuli. Neurophysiological features were correlated with self‐reported data.

Results

VRH condition was associated with lower pain and higher dissociation. VRH significantly decreased amplitudes of N100 and P200 ERP components, reduced EEG power between 1 and 5 Hz from 100 to 560 ms, and increased EEG power from 5 to 11 Hz from 340 to 800 ms. These findings were observed at frontal, central and posterior electrodes. Heart rate variability was significantly higher and breathing frequency reduced with VRH. Correlations were found between the self‐reported level of pain and ERP components.

Conclusion

VRH modulates cerebral pain processes and body physiology, leading to reduced pain levels. These findings offer a first insight on the analgesic mechanisms of VRH and suggest that VRH is an effective approach to reduce experimental pain.

Significance

VRH decreases experimental pain perception, increases subject level of dissociation and modulates cerebral pain processing mechanisms. Pain can be managed with analgesic medication but also through complementary interventions. Among these, hypnosis and virtual reality (VR) are known to reduce pain for patients and healthy individuals. In recent years, an innovative technique combining hypnosis and VR has been proposed to help patients in managing pain. However, to our knowledge, no study has focused on the underlying mechanisms of this VR/hypnosis combination. We showed that VR combined with hypnosis decreases experimental pain, increases dissociation and influences EEG modulation.
Selection of representative natural hazard scenarios for engineering systems
Authors: Rosero‐Velásquez Hugo , Straub Daniel
Published: October 2022

Representative hazard scenarios are essential for many tasks in risk management, such as preparedness and emergency response planning. However, criteria and methods for systematically selecting such scenarios for natural hazards are lacking. From a risk perspective, such scenarios should be selected considering the losses they incur. Hence, we propose to define a scenario that is representative for a certain degree of loss, for example, the 100‐year loss, as the most likely one among all possible scenarios leading to this loss. Taking basis in a generic model of natural hazards and their impact on engineering systems, we formally introduce the representative scenarios. We then develop algorithms that enable an efficient evaluation of these scenarios. The method and algorithms are demonstrated on a hypothetical example considering a spatially distributed infrastructure system subjected to earthquakes.