bluuebunny/crossref_metadata_2025 huggingface dataset:
Comer, beber, amar… y comparar. Análisis contrastivo de la audiodescripción en chino y español: un estudio de caso
Authors:   Departamento de Traducción e Interpretación y de Estudios del Asia Oriental, Universidad Autónoma de Barcelona, Yuchen Liu , Tor-Carroggio Irene ,   Departamento de Traducción e Interpretación y de Estudios del Asia Oriental, Universidad Autónoma de Barcelona
Published: November 2022

El presente artículo lleva a cabo un análisis contrastivo de una audiodescripción en chino y en español para dirimir si las diferencias entre estas dos lenguas y culturas se traducen en guiones de audiodescripción significativamente diferentes. Nuestro estudio de caso se vertebra alrededor de la película Comer, beber, amar de Ang Lee (1994) y su análisis se divide en dos partes: en primer lugar, detectamos las diferencias en las descripciones de los personajes y, en segundo lugar, estudiamos los culturemas, que categorizamos de acuerdo con la propuesta de Molina (2001). A continuación, analizamos las técnicas de traducción empleadas para su traslado partiendo de la clasificación de las técnicas traductoras propuesta por Molina y Hurtado (2002). Los resultados demuestran que existen numerosas diferencias en la manera de audiodescribir entre el par de lenguas escogido, hecho que afecta directamente a la traducción de guiones de audiodescripción, una manera más rápida y barata que podría emplearse en el futuro en China para ofrecer este servicio de accesibilidad.
Sujeto variable de 3.ª persona singular en el habla de Montevideo
Authors:   Departamento de Expresión, Facultad de Artes Liberales, Universidad Adolfo Ibáñez, Martínez-Lara José Alejandro
Published: November 2022

El objetivo de este trabajo es describir la alternancia entre la presencia y ausencia del sujeto de 3.ª persona singular en el dialecto de Montevideo, de manera que puedan aportarse nuevos datos acerca de esta variación morfosintáctica. Este fenómeno consiste en que el sujeto gramatical pueda ser expresado por medio de una forma explícita o implícita en una cláusula personal con verbo conjugado. Para llevar a cabo esta investigación se analizó una muestra de doce entrevistas semidirigidas, pertenecientes al corpus sociolingü.stico de Montevideo, adscrito al PRESEEA. La alternancia se correlacionó con variables lingüísticas —tipología verbal, ambigüedad, turno de la conversación, conectividad discursiva y distancia clausular— y sociales —sexo, edad y grado de instrucción—. Los resultados muestran que el uso de las formas pronominales explícitas de sujeto de 3.ª persona singular se debe a razones discursivas vinculadas a la cohesión textual.
Co-occurrence of Intestinal Parasites among School Children of Akonolinga, Centre Region of Cameroon: Emergency Need to Reduce the Health Divide
Authors: Gael Oyono Martin , Samuel Fosso , Clarisse Njua-Yafi , Gustave Lehman Léopold , Félix Bilong Bilong Charles
Published: November 2022

Background: Intestinal parasitosis pose a serious problem to public health and development, especially for the underprivileged population of low and middle-income countries. School children, who are the most affected, can harbour several parasites at the same time. There is a need to adopt efficient strategies for the elimination of intestinal parasitic infections as a public health problem by 2030.

Methods: This cross-sectional study was conducted to highlight the level of co-occurrence of intestinal parasites among pupils of the Akonolinga locality of the Centre region of Cameroon. Pupils were randomly recruited from 5 public schools; stool samples were collected from those whose parents agreed to participate in the study. Helminth eggs and protozoan cysts were assessed by direct smear and the formol-ether concentration technique.

Results: Out of the 416 pupils recruited, 252 were infected by at least one of the ten intestinal parasites identified. The most frequent soil-transmitted helminths were Ascaris lumbricoides and Trichuris trichiura with prevalences of 21.4 % and 18.5 %, respectively. Entamoeba coli was the main protozoan followed by E. histolytica/dispar with prevalences of 29.3% and 23.8%, respectively, and Embadomonas intestinalis was found in only one pupil (0.2%). The co-occurrence of intestinal parasites reached 50% and children with up to four different parasites were detected. The pair of intestinal protozoan parasites, E. histolytica/dispar and E. coli were the most observed with a frequency of 9.5%. Living in a rural setting and young age were important determinants for most of the parasite infections and co-occurrence of parasites.

Conclusion: The co-occurrence of intestinal parasites among school children of Akonolinga is high, and this situation is more alarming in rural areas and in younger children. The living conditions and the co-occurrence of parasites must be integrated into public policies for fighting against intestinal parasite infections.
Association Between Nephrologist Ownership of Dialysis Facilities and Clinical Outcomes
Authors: Lin Eugene , McCoy Matthew S. , Liu Manqing , Lung Khristina I. , Rapista Derick , Berns Jeffrey S. , Kanter Genevieve P.
Published: November 2022

Importance

Ownership of US dialysis facilities presents a financial conflict of interest for nephrologists, who may change their clinical practice to improve facility profitability.

Objective

To investigate the association between nephrologist ownership of freestanding dialysis facilities and clinical outcomes.

Design, Setting, and Participants

This cross-sectional study was conducted using US Renal Data System data linked to a data set of freestanding nonpediatric dialysis facility owners. Participants were a sample of all adults with fee-for-service Medicare receiving dialysis for end-stage kidney disease from January 2017 to November 2017 at included facilities. Data were analyzed from April 2020 through August 2022.

Exposures

Outcomes associated with nephrologist ownership were assessed using a difference-in-differences analysis comparing the difference in outcomes between patients treated by nephrologist owners and patients treated by nonowners within facilities owned by nephrologists after accounting for differences in patient outcomes between nephrologist owners and nonowners in other facilities.

Main Outcomes and Measures

Outcomes plausibly associated with nephrologist ownership were evaluated: (1) treatment volumes (missed treatments and transplant waitlist status); (2) erythropoietin-stimulating agent (ESA) use and related outcomes (anemia, defined as hemoglobin level <10 g/dL, and blood transfusions), (3) quality metrics (mortality, hospitalizations, 30-day readmissions, hemodialysis adequacy, arteriovenous fistula use, and hemodialysis catheter use for ≥3 months), and (4) home dialysis use.

Results

A cohort of 251 651 patients (median [IQR] age, 66 [46-85] years; 112 054 [44.5%] women; 9765 Asian [3.9%], 86 837 Black [34.5%], and 148 617 White [59.1%]; 38 938 Hispanic [15.5%]) receiving dialysis for end-stage kidney disease were included. Patient treatment by nephrologist owners at their owned facilities was associated with a 2.4 percentage point (95% CI, 1.1-3.8 percentage points) higher probability of home dialysis, a 2.2 percentage point (95% CI, 3.6-0.7 percentage points) lower probability of receiving an ESA, and no significant difference in anemia or blood transfusions. Patient treatment by nephrologist owners at their owned facilities was not associated with differences in missed treatments, transplant waitlisting, mortality, hospitalizations, 30-day readmissions, hemodialysis adequacy, or fistula or long-term dialysis catheter use.

Conclusions and Relevance

This cross-sectional cohort study found that nephrologist ownership was associated with increased home dialysis use, decreased ESA use, and no change in anemia or blood transfusions.
Effect of Computer-Tailored Print Feedback, Motivational Interviewing, and Motivational Enhancement Therapy on Engagement in Advance Care Planning
Authors: Fried Terri R. , Yang Manshu , Martino Steve , Iannone Lynne , Zenoni Maria , Blakley Laura , O’Leary John R. , Redding Colleen A. , Paiva Andrea L.
Published: November 2022

Importance

There is a tension between clinician-led approaches to engagement in advance care planning (ACP), which are effective but resource-intensive, and self-administered tools, which are more easily disseminated but rely on ability and willingness to complete.

Objective

To examine the efficacy of computer-tailored print feedback (CTPF), motivational interviewing (MI), and motivational enhancement therapy (MET) on completion of a set of ACP activities, each as compared with usual care.

Design, Setting, and Participants

This randomized clinical trial was conducted from October 2017 to December 2020 via telephone contact with primary care patients at a single VA facility; 483 veterans aged 55 years or older were randomly selected from a list of patients with a primary care visit in the prior 12 months, with oversampling of women and people from minoritized racial and ethnic groups. Statistical analysis was performed from January to June 2022.

Interventions

Mailed CTPF generated in response to a brief telephone assessment of readiness to engage in and attitudes toward ACP; MI, an interview exploring ambivalence to change and developing a change plan; and MET, MI plus print feedback, delivered by telephone at baseline, 2, and 4 months.

Main Outcome and Measures

Self-reported completion of 4 ACP activities: communicating about views on quality vs quantity of life, assignment of a health care agent, completion of a living will, and submitting documents for inclusion in the electronic health record at 6 months.

Results

The study included 483 persons, mean (SD) age 68.3 (8.0) years, 18.2% women and 31.1% who were people from minoritized racial and ethnic groups. Adjusting for age, education, race, gender, and baseline stage of change for each ACP, predicted probabilities for completing the ACP activities were: usual care 5.7% (95% CI, 2.8%-11.1%) for usual care, 17.7% (95% CI, 11.8%-25.9%; P = .003) for MET, 15.8% (95% CI, 10.2%-23.6%; P = .01) for MI, P = .01, and 10.0% (95% CI, 5.9%-16.7%; P = .18) for CTPF.

Conclusions and Relevance

This randomized clinical trial found that a series of 3 MI and MET counseling sessions significantly increased the proportion of middle-aged and older veterans completing a set of ACP activities, while print feedback did not. These findings suggest the importance of clinical interaction for ACP engagement.

Trial Registration

ClinicalTrials.gov Identifier: NCT03103828
Variations in Use of Diabetes Drugs With Cardiovascular Benefits Among Medicaid Patients
Authors: Zhai Mike Z. , Avorn Jerry , Liu Jun , Kesselheim Aaron S.
Published: November 2022

Importance

Cardiovascular death remains the leading cause of mortality in patients with type 2 diabetes (T2D). A better understanding of the current use and adoption of glucose-lowering drugs with cardiovascular benefit can inform state policies to ensure their appropriate use in patients with T2D.

Objective

To characterize the use of glucose-lowering agents with known cardiovascular benefit over time and across states.

Design, Setting, and Participants

This cross-sectional pharmacoepidemiological study of Medicaid prescription rates of glucose-lowering agents with known cardiovascular benefit vs those with less well-established cardiovascular benefit was conducted between 2014 and 2019. In 50 states and the District of Columbia, the study focused on nonmetformin, noninsulin glucose-lowering drugs divided into 3 cohorts: (1) sodium-glucose cotransporter 2 (SGLT2) inhibitors, (2) glucagon-like peptide 1 (GLP1) receptor agonists, and (3) all other classes of glucose-lowering drugs. Data were analyzed from January 2014 to December 2019.

Main Outcomes and Measures

Number of days supplied of each cohort, use ratios between the aggregated days supplied of glucose-lowering agents with known cardiovascular benefit vs those with less well-established cardiovascular benefit, and the mean change in use ratios per quarter.

Results

Across the 50 states and the District of Columbia, the use ratio of glucose-lowering agents with known cardiovascular benefit ranged from 1.58 to 0.14 (mean [SD], 0.48 [0.27]) in 2019. A lower use ratio was seen in states with a higher prevalence of diabetes (β = −0.049; 95% CI, −0.086 to −0.012; P = .01), a larger total population (β = −0.013; 95% CI, −0.023 to −0.003; P = .01), a greater number of Medicaid enrollees (β = −0.054; 95% CI, −0.096 to −0.014; P = .01), a greater proportion of people enrolled in Medicaid (β = −0.018; 95% CI, −0.030 to −0.007; P = .002), and a greater proportion of Medicaid patients enrolled in managed care organizations (β = −0.0032; 95% CI, −0.0051 to −0.0013; P = .002). Higher Medicaid expenditures per enrollee (β = 0.047; 95% CI, 0.007 to 0.089; P = .03) were associated with a higher use ratio of these agents. The relative use of glucose-lowering agents with known cardiovascular benefit by Medicaid enrollees increased 7.4% per year from 2014 to 2019, with wide variations across state Medicaid programs.

Conclusions and Relevance

In this cross-sectional study, glucose-lowering agents with cardiovascular benefit increased in use during the study period, but also demonstrated considerable variation among states in their relative use. Medicaid programs should try to clarify which factors may be contributing to relative underuse of these potentially life-saving drugs.
Effects of Zn Addition on Microstructural Evolution, Mechanical Properties, and Corrosion Resistance of Al‐6Mg Alloy Subjected to Equal Channel Angular Pressing Processing at 200 °C
Authors: Guo Yanping , Gao Chao , Yang Xiaohui , Ku Tingting , Wang Linzeng , Yang Wenlu , Hu Rujie , Cui Jianyu , Chen Huiqin
Published: November 2022

The evolution of microstructure, mechanical properties, and corrosion performance of Al‐6Mg and Al‐6Mg–1Zn alloys processed using equal channel angular pressing (ECAP) at 200 °C is systematically investigated. Microstructural analysis reveals that different T and β phases are generated in the two studied alloys, resulting in different grain refinement processes. The average size of T phase in Al‐6Mg–1Zn alloy increases first and then decreases, and the distribution of T phase inside grains becomes denser with increasing ECAP deformation. The continuity of T phase at the grain boundary increases from 0 to 2 passes and decreases from 2 to 4 passes. In contrast, the β phase in Al‐6Mg alloy mainly locates at grain boundaries and becomes coarser and more continuous from 0 to 4 passes. The fracture strength of Al‐6Mg–1Zn alloy after 4‐pass ECAP reaches 391 MPa with a fracture elongation of 28%, which is superior to that of 4‐pass ECAP Al‐6Mg alloy. The 4‐pass ECAP Al‐6Mg–1Zn alloy has a higher corrosion resistance compared to the Al‐6Mg alloy under the same deformation condition. The low corrosion susceptibility in 4‐pass ECAP Al‐6Mg–1Zn alloy is attributed to sparse distribution of the T phase along the grain boundary.
Construction of Ordered Atomic Donor–Acceptor Architectures in bcc IrGa Intermetallic Compounds toward Highly Electroactive and Stable Overall Water Splitting
Authors: Zhang Huaifang , Shi Peidong , Ma Xiao , Ma Chaoqun , Han Sumei , He Caihong , Wu Haoming , Zhu Lijie , Zhang Bowei , Lu Yunzhang , Cao Wenbin , Yin Haiqing , Meng Xiangmin , Xia Jing , Zhang Jiangwei , Wang An‐Liang , Lu Qipeng
Published: November 2022

Benefiting from ordered atomic structures and strong d‐orbital interactions, intermetallic compounds (IMCs) are promising electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Herein, the body‐centered cubic IrGa IMCs with atomic donor–acceptor architectures are synthesized and anchored on the nitrogen‐doped reduced graphene oxide (i.e., IrGa/N‐rGO). Structural characterizations and theoretical calculations reveal that the electron‐rich Ir sites are atomically dispersed in IrGa/N‐rGO, facilitating the electron transfer between Ir atoms and adsorbed species, which can efficiently decrease the energy barriers of the potential determining step for both HER and OER. Impressively, the IrGa/N‐rGO||IrGa/N‐rGO exhibits excellent performance for overall water splitting in alkaline medium, requiring a low cell voltage of 1.51 V to achieve 10 mA cm−2, meanwhile, exhibiting no significant degradation for 100 h. This work demonstrates that the rational design of noble metal electrocatalysts with donor–acceptor architectures is beneficial for catalytic reactions in energy conversion applications.
Lithium Borate Ionic Liquids as Single‐Component Electrolytes for Batteries
Authors: Guzmán‐González Gregorio , Alvarez‐Tirado Marta , Olmedo‐Martínez Jorge L. , Picchio Matías L. , Casado Nerea , Forsyth Maria , Mecerreyes David
Published: November 2022

Current electrolytes for lithium batteries are usually composed of at least two chemical compounds, an organic solvent such as a cyclic carbonate and a lithium salt such as LiPF6. Here, the concept of using a single‐component electrolyte is demonstrated in lithium batteries based on new lithium borate ionic liquids at room temperature. The design concept of this class of lithium ionic liquids (LiILs) is based on an asymmetrically substituted central tetracoordinate boron atom with oligoethylene glycol groups, fluorinated electron‐attracting groups, and one alkane group. The optimized borateLi+ LiILs show a high ionic conductivity value of >10−4 S cm−1 at 25 °C, high lithium transference numbers ( = 0.4 – 0.5) and electrochemical stability (>4 V). Some of the LiILs present high compatibility with lithium‐metal electrodes showing stable polarization profiles in platting/stripping tests. The selected LiIL is investigated as single‐component electrolytes in lithium‐metal battery cells showing discharge capacity values in Li0/LiIL/lithium–iron phosphate and Li0/LiIL/lithium titanate cells of 124 and 75 mAh g−1, respectively, at a C‐rate of 0.2 C and 65 °C with low‐capacity loss.
Modeling and Design of Zero‐Stiffness Elastomer Springs Using Machine Learning
Authors: Kim Hyeongkeun , Tawfick Sameh H. , King William P.
Published: November 2022

Architected metamaterials exhibit complex stress–strain responses, such as quasi‐zero stiffness (QZS) plateau response useful in vibration and energy absorption, by exploiting elastic instabilities such as buckling. However, the design of metamaterials with prescribed nonlinear mechanical properties is challenging due to the difficulty in accurately predicting nonlinear mechanical responses such as buckling and self‐contact, as well as geometric and material uncertainties. Herein, additive manufacturing (AM) with machine learning (ML) to demonstrate data‐driven modeling and the design of nonlinear elastomeric springs with a broad stress plateau is combined. 243 elastomer chi (χ) spring parts with different design parameters fabricated by AM are tested. A Gaussian process (GP) model is trained on key features of the measured mechanical response and predicts the mechanical response within a 3% error with as few as 97 parts. To account for the geometric and material uncertainties, the GP model to develop an uncertainty‐aware design optimization approach to tailor the mechanical response based on the covariance matrix adaptation evolution strategy (CMA‐ES) is utilized. Excellent agreement is demonstrated between the designed response and measured response over the range of plateau stress considered. The research illustrates the promise of experimental data‐driven approaches and AM in enabling complex material design.
Midline growth of the sphenoid bone in primates: A histological and microcomputed tomography study
Authors: Wood Brody , Oladipupo Lanre , Mano Nanami , Taylor Jane , Vinyard Christopher J. , Cray James , DeLeon Valerie B. , Smith Timothy D.
Published: November 2022

Objectives

The aim of the present study is to broaden our knowledge of the ontogeny of cranial base cartilaginous joints in primates.

Materials and Methods

A cross‐sectional age sample of 66 specimens from four platyrrhine and three strepsirrhine genera were studied using microcomputed tomography, histology, and immunohistochemistry. Specimens were segmented, reconstructed, and measured using Amira software. Ontogenetic scaling of palatal, presphenoid, and basisphenoid length relative to cranial length was examined using standardized major axis regression. After histological sectioning, selected specimens were examined using immunohistochemistry of antibodies to proliferating cell nuclear antigen.

Results

Our results support the hypothesis that the presphenoid in platyrrhines grows more rapidly compared with strepsirrhines, but this study establishes that most or all of this growth discrepancy occurs prenatally, and mostly at the presphenoseptal synchondrosis (PSept). All species have prolonged patency (here meaning absence of any bony bridging across the synchondrosis) of the intrasphenoidal and spheno‐occipital synchondroses (ISS). However, immunohistochemical results suggest growth is only rapid throughout infancy, and mitotic activity is slowing during juvenile ages. The same is indicated for the PSept.

Discussion

These results demonstrate that platyrrhines and strepsirrhines do not follow the pattern of early fusion of ISS seen in humans. In addition, these primates have a more prolonged patency and growth at PSept compared with humans. Finally, results reveal that in bushbabies and tamarins, as in humans, synchondroses remain cartilaginous for a prolonged period after chondrocyte proliferation has slowed or ceased. In light of these results, it is time to reassess related processes, such as differences in timing of brain expansion.
Rational Design of a Facially CoordinatingP,N,NLigand for Manganese‐Catalysed Enantioselective Hydrogenation of Cyclic Ketones
Authors: Oates Conor L. , Goodfellow Alister S. , Bühl Michael , Clarke Matthew L.
Published: November 2022

DFT calculations on the full catalytic cycle for manganese catalysed enantioselective hydrogenation of a selection of ketones have been carried out at the PBE0‐D3PCM//RI‐BP86PCMlevel. Mn complexes of an enantiomerically pure chiralP,N,Nligand have been found to be most reactive when adopting a facial coordination mode. The use of a new ligand with anortho‐substituted dimethylamino‐pyridine motif has been calculated to completely transform the levels of enantioselectivity possible for the hydrogenation of cyclic ketones relative to the first‐generation Mn catalysts.In silicoevaluation of substrates has been used to identify those likely to be reduced with high enantiomer ratios (er), and others that would exhibit less selectivity; good agreements were then found in experiments. Various cyclic ketones and some acetophenone derivatives were hydrogenated wither'sup to 99 : 1.
Cobalt‐Catalyzed Enantioselective Hydroamination of Arylalkenes with Secondary Amines
Authors: Miao Huanran , Guan Meihui , Xiong Tao , Zhang Ge , Zhang Qian
Published: November 2022

Catalytic asymmetric hydroamination of alkenes with Lewis basic amines is of great interest but remains a challenge in synthetic chemistry. Here, we developed a Co‐catalyzed asymmetric hydroamination of arylalkenes directly using commercially accessible secondary amines. This process enables the efficient access to valuableα‐chiral tertiary amines in good to excellent yields and enantioselectivities. Mechanistic studies suggest that the reaction includes a CoH‐mediated hydrogen atom transfer (MHAT) with arylalkenes, followed by a pivotal catalyst controlled SN2‐like pathway between in situ generated electrophilic cationic alkylcobalt(IV) species and free amines. This radical‐polar crossover strategy not only provides a straightforward and alternative approach for the synthesis of enantioenrichedα‐tertiary amines, but also underpins the substantial opportunities in developing asymmetric radical functionalization of alkenes with various free nucleophiles in oxidative MHAT catalysis.
Rhodium‐katalysierte Anti‐Markovnikov Hydroiodierung von Terminalen Alkinen**
Authors: Boehm Philip , Kehl Niklas , Morandi Bill
Published: November 2022

Wir beschreiben eine Rhodium‐katalysierte anti‐Markovnikov Hydroiodierung von terminalen aromatischen und aliphatischen Alkinen. Je nach Wahl des Liganden und Substrats werden entweder (E)‐ oder (Z)‐konfigurierte Alkenyliodide mit hoher bis ausschließlicher Isomerenreinheit erhalten. Die Reaktion weist ein breites Substratspektrum und eine hohe Toleranz gegenüber funktionellen Gruppen auf, wobei leicht zugängliche oder kommerziell erhältliche aliphatische Iodide als HI‐Äquivalent via einem Shuttle‐Prozess verwendet werden. Die synthetisierten Vinyliodide wurden in mehreren Reaktionen zur Bildung von C−C und C−Heteroatom Bindungen unter vollständiger Beibehaltung der Stereoselektivität eingesetzt. Mit der entwickelten Methode konnte die Totalsynthese einer marinen cis‐Fettsäure deutlich verkürzt werden. Zusätzlich konnten mithilfe von Deuterium‐Markierungsexperimenten und stöchiometrischen Reaktionen erste Informationen über einen möglichen Reaktionsmechanismus erhalten werden.
Large‐area Free‐standing Metalloporphyrin‐based Covalent Organic Framework Films by Liquid‐air Interfacial Polymerization for Oxygen Electrocatalysis
Authors: Tang Jiaqi , Liang Zuozhong , Qin Haonan , Liu Xiangquan , Zhai Binbin , Su Zhen , Liu Qianqian , Lei Haitao , Liu Kaiqiang , Zhao Chuan , Cao Rui , Fang Yu
Published: November 2022

Synthesizing large‐area free‐standing covalent organic framework (COF) films is of vital importance for their applications but is still a big challenge. Herein, we reported the synthesis of large metalloporphyrin‐based COF films and their applications for oxygen electrocatalysis. The reaction of meso‐benzohydrazide‐substituted metal porphyrins with tris‐aldehyde linkers afforded free‐standing COF films at the liquid‐air interface. These films can be scaled up to 3000 cm2 area and display great mechanical stability and structural integrity. Importantly, the Co‐porphyrin‐based films are efficient for electrocatalytic O2 reduction and evolution reactions. A flexible, all‐solid‐state Zn‐air battery was assembled using the films and showed high performance with a charge–discharge voltage gap of 0.88 V at 1 mA cm−2 and high stability under bent conditions (0° to 180°). This work thus presents a strategy to synthesize functionalized COF films with high quality for uses in flexible electronics.
A Platinum(II)‐Based Molecular Cage with Aggregation‐Induced Emission for Enzymatic Photocyclization of Alkynylaniline
Authors: Wei Zhong , Jing Xu , Yang Yang , Yuan Jiayou , Liu Mingxu , He Cheng , Duan Chunying
Published: November 2022

Enzymes facilitate chemical conversions through the collective activity of aggregated components, but the marriage of aggregation‐induced emission (AIE) with molecular containers to emulate enzymatic conversion remains challenging. Herein, we report a new approach to construct a PtII‐based octahedral cage with AIE characteristics for the photocyclization of alkynylaniline by restricting the rotation of the pendant phenyl rings peripheral to the PtII corner. With the presence of water, the C−H⋅⋅⋅π interactions involving the triphenylphosphine fragments resulted in aggregation of the molecular cages into spherical particles and significantly enhanced the PtII‐based luminescence. The kinetically inert Pt‐NP chelator, with highly differentiated redox potentials in the ground and excited states, and the efficient coordination activation of the platinum corner facilitated excellent catalysis of the photocyclization of alkynylaniline. The enzymatic kinetics and the advantages of binding and activating substrates in an aqueous medium provide a new avenue to develop mimics for efficient photosynthesis.
Perfectly Encoding π‐Conjugated Anions in the RE5(C3N3O3)(OH)12 (RE=Y, Yb, Lu) Family with Strong Second Harmonic Generation Response and Balanced Birefringence
Authors: Meng Xianghe , Zhang Xingyu , Liu Qingxiong , Zhou Zhengyang , Jiang Xingxing , Wang Yonggang , Lin Zheshuai , Xia Mingjun
Published: November 2022

Nonlinear optical (NLO) crystal, which simultaneously exhibits strong second‐harmonic‐generation (SHG) response and desired optical anisotropy, is a core optical material accessible to the modern optoelectronics. Accompanied by strong SHG effect in a NLO crystal, a contradictory problem of overlarge birefringence is ignored, leading to low frequency doubling efficiency and poor beam quality. Herein, a series of rare earth cyanurates RE5(C3N3O3)(OH)12 (RE=Y, Yb, Lu) were successfully characterized by 3D electron diffraction technique. Based on a “three birds with one stone” strategy, they enable the simultaneous fulfillment of strong SHG responses (2.5–4.2× KH2PO4), short UV cutoff (ca. 220 nm) and applicable birefringence (ca. 0.15 at 800 nm) by the introduction of rare earth coordination control of π‐conjugated (C3N3O3)3− anions. These findings provide high‐performance short‐wavelength NLO materials and highlight the exploration of cyanurates as a new research area.
Oxidation and Reduction Pathways in the Knowles Hydroamination via a Photoredox‐Catalyzed Radical Reaction**
Authors: Harabuchi Yu , Hayashi Hiroki , Takano Hideaki , Mita Tsuyoshi , Maeda Satoshi
Published: November 2022

Systematic reaction path exploration revealed the entire mechanism of Knowles's light‐promoted catalytic intramolecular hydroamination. Bond formation/cleavage competes with single electron transfer (SET) between the catalyst and substrate. These processes are described by adiabatic processes through transition states in an electronic state and non‐radiative transitions through the seam of crossings (SX) between different electronic states. This study determined the energetically favorable SET path by introducing a practical computational model representing SET as non‐adiabatic transitions via SXs between substrate's potential energy surfaces for different charge states adjusted based on the catalyst's redox potential. Calculations showed that the reduction and proton shuttle process proceeded concertedly. Also, the relative importance of SET paths (giving the product and leading back to the reactant) varies depending on the catalyst's redox potential, affecting the yield.
Controlling Selectivity in Shuttle Hetero‐difunctionalization Reactions: Electrochemical Transfer Halo‐thiolation of Alkynes
Authors: Dong Xichang , Klein Martin , Waldvogel Siegfried R. , Morandi Bill
Published: November 2022

Shuttle hetero‐difunctionalization reaction, in which two chemically distinct functional groups are transferred between two molecules, has long been an unmet goal due to the daunting challenges in controlling the chemo‐, regio‐, and stereoselectivity. Herein, we disclose an electrochemistry enabled shuttle reaction (e‐shuttle) to selectively transfer one RS− and one X− group between β‐halosulfides and unsaturated hydrocarbons via a consecutive paired electrolysis mechanism. The preferential anodic oxidation of one anion over the other, which is controlled by their distinct redox potentials, plays a pivotal role in controlling the high chemoselectivity of the process. This easily scalable methodology enables the construction of a myriad of densely functionalized β‐halo alkenyl sulfides in unprecedented chemo‐, regio‐, and stereoselectivity using benign surrogates, e.g., 2‐bromoethyl sulfide, avoiding the handling of corrosive and oxidative RS–Br reagents. In a broader context, these results open up new strategies for selective shuttle difunctionalization reactions.
Dithiol‐Activated Bioorthogonal Chemistry for Endoplasmic Reticulum‐Targeted Synergistic Chemophototherapy
Authors: Sun Jian , Zhang Xiaoran , Wang Xia , Peng Jinlei , Song Gang , Di Yufei , Feng Fude , Wang Shu
Published: November 2022

The controlled intracellular release of nitrite is still an unmet challenge due to the lack of bio‐friendly donors, and the antitumor effect of nitrite is limited by its physiologically inert activity. Herein, we designed benzothiadiazole‐based organic nitrite donors that are stable against bio‐relevant species but selectively respond to dithiol species through SNAr/intramolecular cyclization tandem reactions in the aqueous media. The bioorthogonal system was established to target the endoplasmic reticulum (ER) of liver cancer HepG2 cells. The nitrite and nonivamide were coupled to induce elevation of intracellular levels of calcium ions as well as reactive oxygen/nitrogen species, which resulted in ER stress and mitochondrial dysfunction. We demonstrated that a combination of photoactivation and “click to release” strategy could enhance antitumor effect in cellular level and show good potential for cancer precision therapy.
Selecting Better Biocatalysts by Complementing Recoded Bacteria**
Authors: Rubini Rudy , Jansen Suzanne C. , Beekhuis Houdijn , Rozeboom Henriëtte J. , Mayer Clemens
Published: November 2022

In vivo selections are powerful tools for the directed evolution of enzymes. However, the need to link enzymatic activity to cellular survival makes selections for enzymes that do not fulfill a metabolic function challenging. Here, we present an in vivo selection strategy that leverages recoded organisms addicted to non‐canonical amino acids (ncAAs) to evolve biocatalysts that can provide these building blocks from synthetic precursors. We exemplify our platform by engineering carbamoylases that display catalytic efficiencies more than five orders of magnitude higher than those observed for the wild‐type enzyme for ncAA‐precursors. As growth rates of bacteria under selective conditions correlate with enzymatic activities, we were able to elicit improved variants from populations by performing serial passaging. By requiring minimal human intervention and no specialized equipment, we surmise that our strategy will become a versatile tool for the in vivo directed evolution of diverse biocatalysts.
Tunable Electrochemical Peptide Modifications: Unlocking New Levels of Orthogonality for Side‐Chain Functionalization
Authors: Karipal Padinjare Veedu Dhanya , Connal Luke A. , Malins Lara R.
Published: November 2022

Electrochemical transformations provide enticing opportunities for programmable, residue‐specific peptide modifications. Herein, we harness the potential of amidic side‐chains as underutilized handles for late‐stage modification through the development of an electroauxiliary‐assisted oxidation of glutamine residues within unprotected peptides. Glutamine building blocks bearing electroactive side‐chain N,S‐acetals are incorporated into peptides using standard Fmoc‐SPPS. Anodic oxidation of the electroauxiliary in the presence of diverse alcohol nucleophiles enables the installation of high‐value N,O‐acetal functionalities. Proof‐of‐principle for an electrochemical peptide stapling protocol, as well as the functionalization of dynorphin B, an endogenous opioid peptide, demonstrates the applicability of the method to intricate peptide systems. Finally, the site‐selective and tunable electrochemical modification of a peptide bearing two discretely oxidizable sites is achieved.
Highly dispersed nano‐copper catalyst on porous polyvinyl chloride for highly regioselective borylation of alkynes
Authors: Xie Wenna , Liu Shiwen
Published: November 2022

We developed a highly regioselective synthesis of multi‐substituted alkenylboronates via a heterogeneous ligand‐free nano‐copper catalyst that was highly dispersed and supported on the porous polyvinyl chloride. In this catalytic system, substituents on the terminal alkynes could affect the configuration of products. Terminal alkynes and general internal alkynes gave β‐selective borylation products, whereas heteroatom‐substituted alkynes like alkynamides, thioacetylenes, and ynol ethers gave α‐selective borylation products in good chemical yields with exclusive regioselectivity.
Discovery of new cinnamic derivatives as anti‐inflammatory agents for treating acute lung injury in mice
Authors: Chen Pengqin , Xu Zhengwei , Wang Xiemin , He Jie , Yang Jun , Wang Jun , Chattipakorn Nipon , Wu Di , Tang Qidong , Liang Guang , Chen Ting
Published: November 2022

The blockade of the overexpression of pro‐inflammatory cytokines by anti‐inflammatory natural products has been proven therapeutically beneficial in the treatment of acute lung injury (ALI). Given the fact that cinnamic acid has been proven to have significant anti‐inflammatory activity, we selected it as a promising lead compound to develop more effective analogs in treating ALI. Learning from the symmetric structure of curcumin, 32 new symmetric cinnamic derivatives were designed, synthesized, and evaluated for their anti‐inflammatory activity. Among them, 6h not only displayed a remarkable inhibitory activity in vitro (85.9% and 65.7% for  IL‐6 and TNF‐α, respectively) without cytotoxicity but also possessed chemical structure stability. Furthermore, an in vivo study in mice revealed that the administration of 6h significantly attenuated lipopolysaccharide‐induced ALI, providing new lead structures for the development of anti‐inflammatory drugs for the treatment of ALI.
Graphic medicine meets human anatomy: The potential role of comics in raising whole body donation awareness in Italy and beyond. A pilot study
Authors: De Stefano Alessia , Rusciano Isabella , Moretti Veronica , Scavarda Alice , Green Michael J. , Wall Shelley , Ratti Stefano
Published: November 2022

Cadaver dissection has always played a fundamental role in medical education. However, especially in Italy, the topic of body donation has remained partially unknown for years. The current study analyses graphic medicine as a new possible communication tool, evaluating and reflecting, with second‐year students enrolled in the International School of Medicine and Surgery at the University of Bologna, about its potentialities for body donation awareness‐raising in both the scientific community and the general population. For the first time in an Italian University, two graphic medicine workshops were organized focusing on human anatomy and body donation. Seminars were positively evaluated by students using a four items Likert‐scale question: mean 3.54 (± SD 0.73) for the Likert question about the experiences of the workshops; 3.88 (± 0.33) for the Likert question regarding the use of graphic medicine in body donation awareness campaigns among the general population; 3.59 (± 0.65) for the Likert question regarding the use of graphic medicine in body donation awareness campaigns among the scientific community. Furthermore, the open‐ended questions included in the anonymous questionnaire were analyzed using the constructivist grounded qualitative analysis, whence various themes emerged. Finally, five graphic medicine projects about body donation were created by students, proving their interest in testing this method to promote body donation, focusing the attention on different communicative aspects. Considering the results of this pilot study, the co‐creative collaborative use of graphic medicine could be evaluated as an additional strategy to increase body donation awareness‐raising in Italy and beyond, especially in the non‐experts' community.
Copolymerization of Carbonyl Sulfide and Propylene Oxide via a Heterogeneous Prussian Blue Analogue Catalyst with High Productivity and Selectivity
Authors: Ullah Khan Munir , Ullah Khan Safir , Cao Xiaohan , Usman Muhammad , Yue Xinchen , Ghaffar Abdul , Hassan Muhammad , Zhang Chengjian , Zhang Xinghong
Published: November 2022

This study demonstrates the superiority of a stable and well‐defined heterogeneous cobalt hexacyanocobaltate (Co3[Co(CN)6]2), a typical cobalt Prussian Blue Analogue (CoCo‐PBA) that catalyzes the copolymerization of carbonyl sulfide (COS) and propylene oxide (PO) to produce poly(propylene monothiocarbonate)s (PPMTC). The number‐average molecular weights of the PPMTC were 66.4 to 139.4 kg/mol, with a polydispersity of 2.0–3.9. The catalyst productivity reached 1040 g polymer/g catalyst (12.0 h). The oxygen‐sulfur exchange reaction (O/S ER), which would generate random thiocarbonate and carbonate units, was effectively suppressed, and thus the selectivity of the monothiocarbonate over carbonate linkages was up to >99%. It was shown that no cyclic thiocarbonate byproduct was produced during the heterogeneous catalysis of COS/PO copolymerization using CoCo‐PBA as the catalyst. The content of monothiocarbonate and ether units in the copolymer chain could be regulated by tuning the feeding amount of COS.
Sorting of cargo in the tubular endosomal network
Authors: Solinger Jachen A. , Spang Anne
Published: November 2022

Intercellular communication is an essential process in all multicellular organisms. During this process, molecules secreted by one cell will bind to a receptor on the cognate cell leading to the subsequent uptake of the receptor‐ligand complex. Once inside, the cell then determines the fate of the receptor‐ligand complex and any other proteins that were endocytosed together. Approximately 80% of endocytosed material is recycled back to the plasma membrane either directly or indirectly via the Golgi apparatus and the remaining 20% is delivered to the lysosome for degradation. Although most pathways have been identified, we still lack understanding on how specificity in sorting of recycling cargos into different pathways is achieved, and how the cell reaches high accuracy of these processes in the absence of clear sorting signals in the bulk of the client proteins. In this review, we will summarize our current understanding of the mechanism behind recycling cargo sorting and propose a model of differential affinities between cargo and cargo receptors/adaptors with regards to iterative sorting in endosomes.
Machine learning with in silico analysis markedly improves survival prediction modeling in colon cancer patients
Authors: Lee Choong‐Jae , Baek Bin , Cho Sang Hee , Jang Tae‐Young , Jeon So‐El , Lee Sunjae , Lee Hyunju , Nam Jeong‐Seok
Published: November 2022

Background

Predicting the survival of cancer patients provides prognostic information and therapeutic guidance. However, improved prediction models are needed for use in diagnosis and treatment.

Objective

This study aimed to identify genomic prognostic biomarkers related to colon cancer (CC) based on computational data and to develop survival prediction models.

Methods

We performed machine‐learning (ML) analysis to screen pathogenic survival‐related driver genes related to patient prognosis by integrating copy number variation and gene expression data. Moreover, in silico system analysis was performed to clinically assess data from ML analysis, and we identified RABGAP1L, MYH9, and DRD4 as candidate genes. These three genes and tumor stages were used to generate survival prediction models. Moreover, the genes were validated by experimental and clinical analyses, and the theranostic application of the survival prediction models was assessed.

Results

RABGAP1L, MYH9, and DRD4 were identified as survival‐related candidate genes by ML and in silico system analysis. The survival prediction model using the expression of the three genes showed higher predictive performance when applied to predict the prognosis of CC patients. A series of functional analyses revealed that each knockdown of three genes reduced the protumor activity of CC cells. In particular, validation with an independent cohort of CC patients confirmed that the coexpression of MYH9 and DRD4 gene expression reflected poorer clinical outcomes in terms of overall survival and disease‐free survival.

Conclusions

Our survival prediction approach will contribute to providing information on patients and developing a therapeutic strategy for CC patients.
The Chromatin Regulator HMGA1a Undergoes Phase Separation in the Nucleus**
Authors: Zhu Hongjia , Narita Masako , Joseph Jerelle A. , Krainer Georg , Arter William E. , Olan Ioana , Saar Kadi L. , Ermann Niklas , Espinosa Jorge R. , Shen Yi , Kuri Masami Ando , Qi Runzhang , Welsh Timothy J. , Collepardo‐Guevara Rosana , Narita Masashi , Knowles Tuomas P. J.
Published: November 2022

The protein high mobility group A1 (HMGA1) is an important regulator of chromatin organization and function. However, the mechanisms by which it exerts its biological function are not fully understood. Here, we report that the HMGA isoform, HMGA1a, nucleates into foci that display liquid‐like properties in the nucleus, and that the protein readily undergoes phase separation to form liquid condensates in vitro. By bringing together machine‐leaning modelling, cellular and biophysical experiments and multiscale simulations, we demonstrate that phase separation of HMGA1a is promoted by protein‐DNA interactions, and has the potential to be modulated by post‐transcriptional effects such as phosphorylation. We further show that the intrinsically disordered C‐terminal tail of HMGA1a significantly contributes to its phase separation through electrostatic interactions via AT hooks 2 and 3. Our work sheds light on HMGA1 phase separation as an emergent biophysical factor in regulating chromatin structure.
Structure‐Dependent Electrical Conductance of DNA Origami Nanowires
Authors: Marrs Jonathan , Lu Qinyi , Pan Victor , Ke Yonggang , Hihath Joshua
Published: November 2022

Exploring the structural and electrical properties of DNA origami nanowires is an important endeavor for the advancement of DNA nanotechnology and DNA nanoelectronics. Highly conductive DNA origami nanowires are a desirable target for creating low‐cost self‐assembled nanoelectronic devices and circuits. In this work, the structure‐dependent electrical conductance of DNA origami nanowires is investigated. A silicon nitride (Si3N4) on silicon semiconductor chip with gold electrodes was used for collecting electrical conductance measurements of DNA origami nanowires, which are found to be an order of magnitude less electrically resistive on Si3N4 substrates treated with a monolayer of hexamethyldisilazane (HMDS) (∼1013 ohms) than on native Si3N4 substrates without HMDS (∼1014 ohms). Atomic force microscopy (AFM) measurements of the height of DNA origami nanowires on mica and Si3N4 substrates reveal that DNA origami nanowires are ∼1.6 nm taller on HMDS‐treated substrates than on the untreated ones indicating that the DNA origami nanowires undergo increased structural deformation when deposited onto untreated substrates, causing a decrease in electrical conductivity. This study highlights the importance of understanding and controlling the interface conditions that affect the structure of DNA and thereby affect the electrical conductance of DNA origami nanowires.
Recent advances in cold atmospheric plasma (CAP) for breast cancer therapy
Authors: Chupradit Supat , Widjaja Gunawan , Radhi Majeed Basman , Kuznetsova Maria , Ansari Mohammad Javed , Suksatan Wanich , Turki Jalil Abduladheem , Ghazi Esfahani Bahar
Published: November 2022

The serious problems of conventional breast cancer therapy strategies such as drug resistance, severe side effects, and lack of selectivity prompted the development of various cold atmospheric plasma (CAP) devices. Due to its advanced technology, CAP can produce a unique environment rich in reactive oxygen and nitrogen species (RONS), photons, charged ions, and an electric field, making it a promising revolutionary platform for cancer therapy. Despite substantial technological successes, CAP‐based therapeutic systems are encounter with distinct limitations, including low control of the generated RONS, poor knowledge about its anticancer mechanisms, and challenges concerning designing, manufacturing, clinical translation, and commercialization, which must be resolved. The latest developments in CAP‐based therapeutic systems for breast cancer treatment are discussed in this review. More significantly, the integration of CAP‐based medicine approaches with other breast cancer therapies, including chemo‐ and nanotherapy is thoroughly addressed.
Black liver in a patient with Wilson's disease
Authors: Jiang Wei , Zeng Qingmin , Liu Chang‐Hai , Wu Dongbo , Tang Hong
Published: November 2022

Wilson's disease is an autosomal recessive inherited disease with congenital copper metabolism disorder, characterized by decreased ceruloplasmin and increased urine copper, which can involve multiple organs. This case was complicated by iron overload, which is of great value in differentiating hereditary hemochromatism.