bluuebunny/crossref_metadata_2025 huggingface dataset:
Nine‐Electron Transfer of Binder Synergistic π‐d Conjugated Coordination Polymers as High‐Performance Lithium Storage Materials
Authors: Wu Yiwen , Shen Jiadong , Sun Zhaoyu , Yang Yan , Li Fangkun , Ji Shaomin , Zhu Min , Liu Jun
Published: December 2022

To solve the problems such as the dissolution and the poor conductivity of organic small molecule electrode materials, we construct π‐d conjugated coordination polymer Ni‐DHBQ with multiple redox‐active centers as lithium storage materials. It exhibits an ultra‐high capacity of 9‐electron transfers, while the π‐d conjugation and the laminar structure inside the crystal ensure fast electron transport and lithium ion diffusion, resulting in excellent rate performance (505.6 mAh g−1 at 1 A g−1 after 300 cycles). The interaction of Ni‐DHBQ with the binder CMC synergistically inhibits its dissolution and anchors the Ni atoms, thus exhibiting excellent cycling stability (650.7 mAh g−1 at 0.1 A g−1 after 100 cycles). This work provides insight into the mechanism of lithium storage in π‐d conjugated coordination polymers and the synergistic effect of CMC, which will contribute to the molecular design and commercial application of organic electrode materials.
A Conformational Restriction Strategy for the Control of CRISPR/Cas Gene Editing with Photoactivatable Guide RNAs**
Authors: Sun Ying‐Jie , Chen Wen‐Da , Liu Ji , Li Jun‐Jin , Zhang Yu , Cai Wei‐Qi , Liu Li , Tang Xin‐Jing , Hou Jian , Wang Ming , Cheng Liang
Published: December 2022

The CRISPR/Cas system is one of the most powerful tools for gene editing. However, approaches for precise control of genome editing and regulatory events are still desirable. Here, we report the spatiotemporal and efficient control of CRISPR/Cas9‐ and Cas12a‐mediated editing with conformationally restricted guide RNAs (gRNAs). This approach relied on only two or three pre‐installed photo‐labile substituents followed by an intramolecular cyclization, representing a robust synthetic method in comparison to the heavily modified linear gRNAs that often require extensive screening and time‐consuming optimization. This tactic could direct the precise cleavage of the genes encoding green fluorescent protein (GFP) and the vascular endothelial growth factor A (VEGFA) protein within a predefined cutting region without notable editing leakage in live cells. We also achieved light‐mediated myostatin (MSTN) gene editing in embryos, wherein a new bow‐knot‐type gRNA was constructed with excellent OFF/ON switch efficiency. Overall, our work provides a significant new strategy in CRISPR/Cas editing with modified circular gRNAs to precisely manipulate where and when genes are edited.
Electrostatic Shielding Boosts Electrochemical Performance of Alloy‐Type Anode Materials of Sodium‐Ion Batteries
Authors: Zheng Cheng , Ji Deluo , Yao Qian , Bai Zhongchao , Zhu Yansong , Nie Chuanhao , Liu Duo , Wang Nana , Yang Jian , Dou Shixue
Published: December 2022

The applications of alloy‐type anode materials for Na‐ion batteries are always obstructed by enormous volume variation upon cycles. Here, K+ ions are introduced as an electrolyte additive to improve the electrochemical performance via electrostatic shielding, using Sn microparticles (μ‐Sn) as a model. Theoretical calculations and experimental results indicate that K+ ions are not incorporated in the electrode, but accumulate on some sites. This accumulation slows down the local sodiation at the “hot spots”, promotes the uniform sodiation and enhances the electrode stability. Therefore, the electrode maintains a high specific capacity of 565 mAh g−1 after 3000 cycles at 2 A g−1, much better than the case without K+. The electrode also remains an areal capacity of ≈3.5 mAh cm−2 after 100 cycles. This method does not involve time‐consuming preparation, sophisticated instruments and expensive reagents, exhibiting the promising potential for other anode materials.
Dearomatization of Biaryls through Polarity Mismatched Radical Spirocyclization
Authors: Azpilcueta‐Nicolas Carlos R. , Meng Derek , Edelmann Simon , Lumb Jean‐Philip
Published: December 2022

Dearomatization reactions involving radical cyclizations can facilitate the synthesis of complex polycyclic systems that find applications in medicinal chemistry and natural product synthesis. Here we employ redox‐neutral photocatalysis to affect a radical spirocyclization that transforms biaryls into spirocyclic cyclohexadienones under mild reaction conditions. In a departure from previously reported methods, our work demonstrates the polarity mismatched addition of a nucleophilic radical to an electron rich arene, and allows the regioselective synthesis of 2,4‐ or 2,5‐cyclohexadienones with broad functional group tolerance. By transforming biaryls into spirocycles, our methodology accesses underexplored three‐dimensional chemical space, and provides an efficient means of creating quaternary spirocenters that we apply to the first synthesis of the cytotoxic plant metabolite denobilone A.
Isomeric Oligo(Phenylenevinylene)‐Based Covalent Organic Frameworks with Different Orientation of Imine Bonds and Distinct Photocatalytic Activities
Authors: Dong Wenbo , Qin Zhiying , Wang Kuixing , Xiao Yueyuan , Liu Xiangyang , Ren Shijie , Li Longyu
Published: December 2022

Imine‐linked covalent organic frameworks (COFs) have been extensively studied in photocatalysis because of their easy synthesis and excellent crystallinity. The effect of imine‐bond orientation on the photocatalytic properties of COFs, however, is still rarely studied. Herein, we report two novel COFs with different orientations of imine bonds using oligo(phenylenevinylene) moieties. The COFs showed similar structures but great differences in their photoelectric properties. COF‐932 demonstrated a superior hydrogen evolution performance compared to COF‐923 when triethanolamine was used as the sacrificial agent. Interestingly, the use of ascorbic acid led to the protonation of the COFs, further altering the direction of electron transfer. The photocatalytic performances were increased to 23.4 and 0.73 mmol g−1 h−1for protonated COF‐923 and COF‐932, respectively. This study provides a clear strategy for the design of imine‐linked COF‐based photocatalysts and advances the development of COFs.
Ru complexes containingN‐methyl‐1,3,5‐triaza‐7‐phosphaadamantane (mPTA) as catalysts for the isomerization of 2‐cyclohexen‐1‐ol
Authors: López‐Sánchez Belén , Bohome‐Espinosa Ana Belén , Scalambra Franco , Romerosa Antonio
Published: December 2022

The complex [RuCp(H2O‐κO)(mPTA)2](CF3SO3)3·MeOH (4·MeOH) was synthesized and characterized by spectroscopic techniques and its crystal structure determined by single‐crystal X‐ray diffraction (mPTA = N‐methyl‐1,3,5‐triaza‐7‐phosphaadamantane). The catalytic activity of4for the redox isomerization of 2‐cyclohexen‐1‐ol into cyclohexanone was studied in water, methanol/water, and biphasic systems, reaching the highest conversion rate in biphasic water/cyclohexane (1:1) at pH 1.7 and under N2. The aqueous phase containing4was recycled up to 7 consecutive runs, reaching a total turnover number (TON) of 471 without significant losses of catalyst. Therefore, this reaction is a unique procedure for the isomerization of cyclic allylic alcohols without metal contamination of the product. The catalytic reaction mechanism was studied by nuclear magnetic resonance (NMR), showing that the reaction probably proceeds through the formation of an intermediate in which the substrate is η2‐coordinated to the metal.
An entropy‐centric equilibrium cooperative theory for the melting behavior of nonideal triaclylglycerol mixtures
Authors: Marangoni Alejandro G. , Ghazani Saeed M. , Pensini Erica
Published: December 2022

A new nonideal, equilibrium thermodynamics model was developed for the prediction of the solid fat content (SFC) of edible fats, which are mixtures of triaclylglycerols (TAGs). The SFC is the most dominant material structural parameter which influences macroscopic mechanical properties and functionality in foods, cosmetics and pharmaceutical incipients. By taking into consideration the entropy of mixing and the activity coefficient of a TAG in an effective solid medium, we calculate a freezing point depression. The new melting point is then nested into an equilibrium expression for the melting of that TAG in such effective solid medium. The model assumes that complex mixtures of TAGs consist of one solid phase in a specific polymorphic form and one liquid phase, obeying mass balances and the overall TAG composition determined experimentally. The SFC is then just the summation of the amount of solid TAG components in the mixture. Novel insights are gained from estimates of a cooperativity index for the melting of the different TAGs in the effective solid medium, while estimated solid‐state activity coefficients speak to interactions of particular TAGs with the effective medium. The model was successfully fitted to eight different SFC‐temperature profiles of complex fats and parameter estimates obtained and interpreted.
A review of research and application of polylactic acid composites
Authors: Li Xiangrui , Lin Yu , Liu Mingli , Meng Lipeng , Li Chunfeng
Published: December 2022

Polylactic acid (PLA) is a thermoplastic polyester that has received widespread attention for its environmentally friendly origin and excellent performance, and its potential to address the current problems of severe white pollution and scarcity of petroleum resources. This article focuses on the synthesis, modification, degradation and application of PLA. The main focus is on the modification of PLA with different environmentally friendly materials (natural organic materials, biodegradable polymers, inorganic minerals) in blends for defects such as the brittleness of PLA. In addition, the applications of PLA composites in the fields of construction, medical, packaging and oil and water separation are also introduced, which hopefully will provide some help to the promotion of PLA.
Improving toughness of epoxy resin by in‐situ formed secondary network during tertiary amine initiated curing
Authors: Tian Nan , Zhao Shuo , Liu Yanping
Published: December 2022

The mechanical properties of epoxy resin cured by tertiary amine initiated ring‐open reaction were investigated. Special curing procedures that first at 130°C for different times (facilitating chain transfer/reducing crosslinking density) and then 80°C/2 h–130°C/2 h were used. For cured specimens, the glass transition temperature showed a continuous decrease with increasing time at the first step of curing (t1st step), and the swelling ratio also increased. These changes pointed to a monotonic decrease in crosslinking density. Mechanical properties were characterized by three‐point bending and tensile test. Both the deflection and strain at break showed a sudden increase when t1st step reached 30 min, corresponding well to occurrence of gelation at 130°C. The fracture surface after tensile test was further examined. Rough surface with rupture of fibrillar structure was found when t1st step reached 30 min. These observations all suggest an abrupt increase of toughness related to gelation (t1st step = 30 min). It is explained by formation of network at the first step of curing, which has lower crosslinking density and serves as a secondary toughening network.
Vascular dodecanoic acid of Arabidopsis mediates an insect resistance against Myzus persicae
Authors: Mallick Moumita , Mondal Hossain A.
Published: December 2022

The present study explores the compatible interaction between Arabidopsis thaliana and Myzus persicae to reduce host resistance from the previous aphid herbivore‐mediated priming. The resumption of host resistance from the “reduced host resistance” was also recorded in due time when aphid herbivore was removed from leaf foliage. The vascular sap, isolated from the midpoint timing from the “reduced host resistance” to the “resumed host resistance” phase resolved in gas chromatography‐mass spectrometry (GC‐MS) analysis that identified an enrichment of dodecanoic acid (DA), an antibacterial metabolite and a saturated medium‐chain fatty acid with a 12‐carbon backbone. DA infiltration into leaf foliage revealed a significant reduction of aphid clonal proliferation on leaf foliage with concomitant reduction of the vascular microbiota titer as well as aphid body. The “resumed host resistance” from “reduced host resistance” also showed a comparable microbiota titer in comparison to control but the “reduced host resistance” evidenced a significant higher microbiota titer which was correlated with an enhanced aphid clonal proliferation on the leaf foliage. The DA infiltrated leaf foliage had no effect on total vascular sap ingestion by the aphid herbivore but induced RNA level of GUS expression under the control of promoter of pad‐4, mpl‐1, and sag‐13. A similar pattern of gus expression was recorded from aphid herbivore. Thus, DA mediates aphid resistance toward aphid clonal proliferation in the host plant by manipulating vascular and aphid body microbiota titer.
On the added benefit of virtual anatomy for dissection‐based skills
Authors: Niedermair Julian F. , Antipova Veronica , Manhal Simone , Siwetz Martin , Wimmer‐Röll Monika , Hammer Niels , Fellner Franz A.
Published: December 2022

Technological approaches deploying three‐dimensional visualization to integrate virtual anatomy are increasingly used to provide medical students with state‐of‐the‐art teaching. It is unclear to date to which extent virtual anatomy may help replace the dissection course. Medical students of Johannes Kepler University attend both a dissection and a virtual anatomy course. This virtual anatomy course is based on Cinematic Rendering and radiological imaging and teaches anatomy and pathology. This study aims to substantiate student benefits achieved from this merged teaching approach. Following their dissection course, 120 second‐year students took part in objective structured practical examinations (OSPE) conducted on human specimens prior to and following a course on Cinematic Rendering virtual anatomy. Likert‐based and open‐ended surveys were conducted to evaluate student perceptions of both courses and their utility. Virtual anatomy teaching was found to be unrelated to improvements in student's ability to identify anatomical structures in anatomical prosections, yielding only a 1.5% increase in the OSPE score. While the students rated the dissection course as being more important and impactful, the virtual anatomy course helped them display the learning content in a more comprehensible and clinically applicable way. It is likely that Cinematic Rendering‐based virtual anatomy affects knowledge gain in domains other than the recognition of anatomical structures in anatomical prosections. These findings underline students' preference for the pedagogic strategy of the dissection course and for blending this classical approach with novel developments like Cinematic Rendering, thus preparing future doctors for their clinical work.
Histology as a paradigm for a science‐based learning experience: Visits by histology education spirits of past, present, and future
Authors: Hortsch Michael
Published: December 2022

The term “histology” was coined a little over 200 years ago and the subject has always relied on microscopy as its defining technology. Microscopy was and still is an essential approach for the description of cellular components and their arrangements in living organisms. For more than a century and a half, histology or microanatomy has also been part of the basic science education for biomedical students. Traditionally, it has been taught in two major components, a didactic transfer of information, either in a lecture or self‐learning format, and in active‐learning laboratory sessions. These two modes of histology instruction conform with the dual‐processing theory of learning, one being more automatic and depending mainly on rote memorization, whereas the other is analytical, requiring more advanced reasoning skills. However, these two components of histology education are not separate and independent, but rather complementary and part of a multi‐step learning process that encourages a scientific analysis of visual information and involves higher‐level learning skills. Conventional, as well as modern electronic instruction methods (e‐learning) have been used in complementary ways to support the integrated succession of individual learning steps as outlined in this manuscript. However, as recent curricular reforms have curtailed instructional time, this traditional format of teaching histology is no longer sustainable and a reflective reassessment of the role of histology in modern biomedical education is a timely necessity.
Effectiveness of eye movement exercise and diaphragmatic breathing with jogging in reducing migraine symptoms: A preliminary, randomized comparison trial
Authors: Rahimi Mohammad Dawood , Hassani Pouriya , Kheirkhah Mohammad Taghi , Fadardi Javad Salehi
Published: December 2022

Background

Migraine is a multifactorial headache disorder. Maladaptive functional networks or altered circuit‐related connectivity in the brain with migraine appear to perturb the effects of usual treatments.

Objectives

In the present preliminary trial, we aim to study the effectiveness of performing pieces of body–mind, cognitive, or network reconstruction‐based training (i.e., eye movement exercise plus jogging; EME+J and diaphragmatic breathing plus jogging; DB+J) in decreasing migraine symptoms.

Methods

We used a three‐arm, triple‐blind, non‐inferiority randomized comparison design with pre‐test, post‐test, and follow‐up measurements to assess the effectiveness of EME+J and DB+J in the brain with migraine. Participants were randomly assigned to one of the study groups to perform either 12 consecutive weeks of EME+J (n = 22), DB+J (n = 19), or receiving, treatment as usual, TAU (n = 22).

Results

The primary outcome statistical analysis through a linear mixed model showed a significant decrease in the frequency (p = .0001), duration (p = .003), and intensity (p = .007) of migraine attacks among the interventions and measurement times. The pairwise comparisons of simple effects showed that EME+J and DB+J effectively reduced migraine symptoms at the post‐test and follow‐up (p < .05). Cochran's tests showed that interventions decreased the number of menses‐related migraine attacks. EME+J and DB+J effectively decreased over‐the‐counter (OTC) drug use, refreshed wake‐up mode, and improved sleep and water drinking patterns. These are the secondary outcomes that Cochran's tests showed in the interventional groups after the interventions and at 12 months of follow‐up.

Conclusion

EME+J or DB+J can be an effective and safe method with no adverse effects to decrease the symptoms of migraine attacks. Moreover, a reduction in the frequency of menstrual cycle‐related attacks, OTC drug use, and improved quality of sleep and drinking water were the secondary outcomes of the post‐test and a 12‐month follow‐up.
Design and Synthesis of Xanthone Analogues Conjugated with Aza‐aromatic Substituents as Promising G‐Quadruplex Stabilizing Ligands and their Selective Cancer Cell Cytotoxic Action
Authors: Roy Soma , Chakraborty Nirmal , Maiti Bappa , Muniyappa Kalappa , Bhattacharya Santanu
Published: December 2022

We have examined the stabilization of higher‐order noncanonical G‐quadruplex (G4) DNA structures formed by the G‐rich sequences in the promoter region of oncogenes such as c‐MYC, c‐KIT, VEGF and BCl2 by newly synthesized, novel nitrogen‐containing aromatics conjugated to xanthone moiety. Compounds with N‐heterocyclic substituents such as pyridine (XNiso), benzimidazole (XBIm), quinoxaline (XQX) and fluorophore dansyl (XDan) showed greater effectiveness in stabilizing the G4 DNA as well as selective cytotoxicity for cancer cells (mainly A549) over normal cells both in terms of UV‐Vis spectral titrations and cytotoxicity assay. Both fluorescence spectral titrimetric measurements and circular dichroism (CD) melting experiments further substantiated the G4 stabilization phenomenon by these small‐molecular ligands. In addition, these compounds could induce the formation of parallel G4 structures in the absence of any added salt condition in Tris⋅HCl buffer at 25 °C. In a polymerase stop assay, the formation of stable G4 structures in the promoter of oncogenes and halting of DNA synthesis in the presence of the above‐mentioned compounds was demonstrated by using oncogene promoter as the DNA synthesis template. Apoptosis‐mediated cell death of the cancer cells was proved by Annexin V‐PI dual staining assay and cell‐cycle arrest occurred in the S phase of the cell cycles. The plausible mode of binding involves the stacking of the xanthone core on the G4 DNA plane with the possibility of interaction with the 5’‐overhang as indicated by molecular dynamics simulation studies.
Synthesis of Uronic Acid 1‐Azasugars as Putative Inhibitors of α‐Iduronidase, β‐Glucuronidase and Heparanase**
Authors: Doherty Gareth G. , Ler Geraldine Jia Ming , Wimmer Norbert , Bernhardt Paul V. , Ashmus Roger A. , Vocadlo David J. , Armstrong Zachary , Davies Gideon J. , Maccarana Marco , Li Jin‐ping , Kayal Yasmin , Ferro Vito
Published: December 2022

1‐Azasugar analogues of l‐iduronic acid (l‐IdoA) and d‐glucuronic acid (d‐GlcA) and their corresponding enantiomers have been synthesized as potential pharmacological chaperones for mucopolysaccharidosis I (MPS I), a lysosomal storage disease caused by mutations in the gene encoding α‐iduronidase (IDUA). The compounds were efficiently synthesized in nine or ten steps from d‐ or l‐arabinose, and the structures were confirmed by X‐ray crystallographic analysis of key intermediates. All compounds were inactive against IDUA, although l‐IdoA‐configured 8 moderately inhibited β‐glucuronidase (β‐GLU). The d‐GlcA‐configured 9 was a potent inhibitor of β‐GLU and a moderate inhibitor of the endo‐β‐glucuronidase heparanase. Co‐crystallization of 9 with heparanase revealed that the endocyclic nitrogen of 9 forms close interactions with both the catalytic acid and catalytic nucleophile.
Understanding and targeting anoikis in metastasis for cancer therapies
Authors: Sattari Fard Farzad  , Jalilzadeh Nazila , Mehdizadeh Amir , Sajjadian Fakhrosadat , Velaei Kobra
Published: December 2022

The development of effective treatments for cancers requires investigations for a more detailed and comprehensive understanding of the basic cellular mechanisms involved in carcinogenesis, cancer progression, and metastasis. One of those driving mechanisms is anoikis, a special type of apoptosis, which is induced by losing anchorage from the extracellular matrix (ECM). In other words, resisting death in detached cells (cells without ECM) forms an anoikis‐resistant phenotype. Since the anoikis‐resistance state compensates for the initial steps of cancer metastasis, this review aimed to discuss mechanisms of gaining anoikis/anoikis resistance phenotype in tumor cells. Finally, we highlighted the significance of anoikis in malignancies so as to provide clear insight into cancer diagnosis and therapy development.
Low‐dose dexamethasone promotes osteoblast viability by activating autophagy via the SGK1/FOXO3a signaling pathway
Authors: Yu Xiang‐Hua , Xu Xiao‐Ming , Zhang Sheng‐Xiang
Published: December 2022

Autophagy contributes to bone homeostasis and development under physiological conditions. Although previous studies have demonstrated the induction of the autophagy machinery by endogenous glucocorticoids (GCs), the precise mechanisms involved have not yet been clarified. The current study aimed to explore the effect of a low dose of GC (10−8 M dexamethasone, Dex) on autophagy in mouse embryonic osteoblastic precursor cells (MC3T3‐E1 cells) and the potential mechanisms. The results showed that 10−8 M Dex induced significant time‐dependent increases in the expression and activation of serum‐ and glucocorticoid‐induced kinase‐1 (SGK1) in MC3T3‐E1 cells and that these effects were accompanied by increased cell viability and decreased apoptosis. The autophagy inhibitor 3‐MA significantly inhibited Dex‐mediated promotion of viability. Moreover, Dex increased LC3II and Beclin‐1 levels and decreased SQSTM/p62 levels in a time‐dependent manner, and these effects were attenuated by pretreatment with 3‐MA. Transfection of Dex‐treated MC3T3‐E1 cells with shRNA‐SGK1 resulted in a significant reduction in cell viability and an increase in apoptosis. 3‐MA further exacerbated these effects of SGK1 inhibition. Knocking down SGK1 before Dex exposure significantly reduced the phosphorylated forkhead box O3a (p‐FOXO3a)/FOXO3 ratio, suppressed LC3II and Beclin‐1 levels, and increased SQSTM/p62 levels in MC3T3‐E1 cells, and these effects were amplified by 3‐MA. In conclusion, the results revealed that low‐dose GC treatment increased osteoblast viability by activating autophagy via the SGK1/FOXO3a pathway.
A novel comprehensive radiation shielding system eliminates need for personal lead aprons in the catheterization laboratory
Authors: Rabah Maher , Allen Sorcha , Abbas Amr E. , Dixon Simon
Published: December 2022

Objectives

This clinical study evaluated the efficacy of a novel radiation shielding system for the cardiac catheterization laboratory designed to provide comprehensive protection that obviates the need for personal lead aprons.

Background

Invasive Cardiologists are exposed to occupational health hazards related directly to radiation exposure (RE) and indirectly to the orthopedic burden of wearing only partially protective lead aprons. Innovations to reduce these risks are warranted. A novel comprehensive shielding system (ProtegoTM, Image Diagnostics Inc, Fitchburg, Ma) has been validated in pre‐clinical studies to provide excellent radiation protection, sufficient for the State of Michigan to certify it for use without need for personal lead aprons.

Methods

This clinical analysis measured RE to a single Physician operator utilizing the ProtegoTM shield (and not wearing personal lead apron) during routine cardiac catheterization procedures (diagnostic and interventional). RE was measured at both thyroid and waist level with a real‐time dosimetry system (RaysafeTM, Billdal, Sweden), calculated on a median per case basis (mrems). Additional parameters collected included procedure type, access site, per case fluoroscopy time, and patient factors including body mass index.

Results

In n=98 cases (25% diagnostic, 75% interventional including 22% chronic total occlusions), median/case RE was 0.4 mrems (thyroid) and 0.2 mrems (waist). RE=0 in 12 cases. In no case did radiation exposure exceed 3.2 mrems.

Conclusion

The ProtegoTM shield system provides excellent RE protection to the Physician operator, without the need for personal lead aprons and has the potential to reduce catheterization laboratory occupational health hazards.
Aortic annulus ellipticity and outcomes after transcatheter aortic valve implantation
Authors: Tomii Daijiro , Okuno Taishi , Lanz Jonas , Stortecky Stefan , Windecker Stephan , Pilgrim Thomas
Published: December 2022

Background

Elliptical shape of the aortic annulus has been associated with an increased risk of device failure after transcatheter aortic valve implantation (TAVI) compared with a circular annular shape.

Aims

To assess the impact of annulus ellipticity on procedural outcomes and device performance in patients undergoing TAVI.

Methods

In a prospective TAVI registry, aortic annulus ellipticity was assessed by preprocedural multidetector computed tomography. The annulus ratios, defined by the ratio of minimum and maximum annulus diameters measured in a transverse double oblique plane, were split into tertiles for comparisons between groups.

Results

A total of 1732 patients undergoing TAVI between August 2007 and June 2020 were included in the present analysis. Patients in the tertile with the most elliptical shape of the annulus were more likely to be female (59.7% vs. 47.9%; p < 0.001) and had a higher Society of Thoracic Surgeons Predicted Risk of Mortality (5.4 ± 3.8 vs. 4.8 ± 3.5; p = 0.002). There were no significant differences in the rate of technical success (95.3% vs. 96.5%; p = 0.235), device success (83.6% vs. 86.5%; p = 0.118) and intended valve performance (90.7% vs. 91.7; p = 0.503) between patients in the most elliptical tertile and the rest. However, valve dislocation/embolization occurred more frequently in patients with elliptical as compared to circular annular shape (2.6% vs. 1.2%; p = 0.046).

Conclusions

Ellipticity of the aortic annulus does not affect procedural and device outcomes in patients undergoing TAVI irrespective of transcatheter heart valve design and generation. https:www.//clinicaltrials.gov. NCT01368250.
Molecular Rotational Correlation Times and Nanoviscosity Determined by 111mCd Perturbed Angular Correlation (PAC) of γ‐rays Spectroscopy
Authors: Fromsejer Rasmus , Jensen Marianne L. , Zacate Matthew O. , Karner Victoria L. , Pecoraro Vincent L. , Hemmingsen Lars
Published: December 2022

The nanoviscosity experienced by molecules in solution may be determined through measurement of the molecular rotational correlation time, τc, for example, by fluorescence and NMR spectroscopy. With this work, we apply PAC spectroscopy to determine the rate of rotational diffusion, λ=1/τc, of a de novo designed protein, TRIL12AL16C, in solutions with viscosities, ξ, from 1.7 to 88 mPa⋅s. TRIL12AL16C was selected as molecular probe because it exhibits minimal effects due to intramolecular dynamics and static line broadening, allowing for exclusive elucidation of molecular rotational diffusion. Diffusion rates determined by PAC data agree well with literature data from fluorescence and NMR spectroscopy, and scales linearly with 1/ξ in agreement with the Stokes–Einstein–Debye model. PAC experiments require only trace amounts (∼1011) of probe nuclei and can be conducted over a broad range of sample temperatures and pressures. Moreover, most materials are relatively transparent to γ‐rays. Thus, PAC spectroscopy could find applications under circumstances where conventional techniques cannot be applied, spanning from the physics of liquids to in‐vivo biochemistry.
Electrocatalytic Reduction of CO2 Coupled with Organic Conversion to Selectively Synthesize High‐Value Chemicals
Authors: Zhong Wanfu , Huang Wenhao , Ruan Sunhong , Zhang Qinghong , Wang Ye , Xie Shunji
Published: December 2022

The electrochemical process of coupling electrocatalytic CO2 reduction and organic conversion reaction can effectively reduce the reaction overpotential and obtain value‐added chemicals. Moreover, because of the diversity of substrates and the designability of coupling forms, more and more attention has been paid to this field. This review systematically summarizes the research progress of coupling electrolysis in recent years, (1) co‐electrolysis of CO2 and organics at the cathode to obtain specific products with high selectivity, (2) replacing traditional anodic oxygen evolution reaction (OER) with other valuable oxidation reactions to improve energy utilization efficiency and economic benefits of CO2 conversion, (3) in an electrolytic cell without membrane, the cathode and anode jointly transform CO2 and organics to redox products. We hope that the examples and insights on coupling electrolysis introduced in this review can inspire researchers to further explore and innovate in this direction.
Synthesis of 3‐Thiocyanobenzothiophene via Difunctionalization of Active Alkyne Promoted by Electrochemical‐Oxidation
Authors: Zhang Dong , Yang Qijun , Cai Jinlin , Ni Chunjie , Wang Qingdong , Wang Qingming , Yang Jinming , Geng Rongqing , Fang Zheng
Published: December 2022

A novel and green method for the synthesis of 3‐thiocyanatobenzothiophenes via electrochemical‐oxidation promoted difunctionalization of active alkyne has been developed. In this protocol, inexpensive and easily available potassium thiocyanate was chosen as the thiocyanation reagent, 2‐alkynylthioanisoles as the substrates, a variety of 3‐thiocyanatobenzothiophenes were obtained in moderate to good yields under oxidant‐ and catalyst‐free conditions. Moreover, the continuous flow system has good applicability for this transformation, the use of continuous flow system has overcome the disadvantage of low efficiency in traditional electrochemical amplification, and realized the stable and excellent yields of target products in the scale‐up reactions.
Visible Light Thiyl Radical‐Mediated Desilylation of Arylsilanes
Authors: Kuhlmann Jan H. , Dickoff Jan H. , Mancheño Olga García
Published: December 2022

A straightforward, visible‐light triggered desilylation of arylsilanes by thiyl radicals is presented. Silyl groups are often used to block a reactive position in multi‐step organic synthesis, for which a mild cleavage at a late‐stage will provide new possibilities and disconnection routes by CAr−Si cleavage/deprotection. In this work, commercially available and cheap disulfides are employed for the first time in this type of C(sp2)‐Si bond cleavage reactions. Thus, upon irradiation with visible‐light, homolytic cleavage of the disulfide give rise to the corresponding thiyl radical that allows for a radical chain mechanism. This methodology represents a mild, fast and simple approach suitable for a broad variety of simply substituted arylsilanes. Moreover, the procedure could be easily extended to natural products and therapeutic derivatives, showing its robustness and synthetic application potential.
Insights into the Photodynamics of Fluorescence Emission and Singlet Oxygen Generation of Fluorogen Activating Protein‐Malachite Green Systems
Authors: Deng Ziqi , Li Lan , Jia Han , Li Nga‐Fong , He Jiaxing , Li Ming‐De , Phillips David Lee , Li Ying
Published: December 2022

The self‐assembled fluorogen activating protein (FAP)‐malachite green (MG) complex is a well‐established protein‐ligand system, which can realize binding‐caused fluorescence turn‐on of MG and singlet oxygen (1O2) generation by MG iodination. To clarify the mechanism of fluorescence activation and 1O2 generation, the photodynamics of different halogen‐substituted MG derivatives and their corresponding FAP‐MG complexes were studied by femtosecond transient absorption spectroscopy and theoretical computations. The results show that the rotation of MG is restricted by FAP binding, which prevents a rapid internal conversion to allow a longer lifetime for the excited MG to undergo fluorescence emission and intersystem crossing. Moreover, these FAP‐MG complexes exhibit notably varied fluorescence quantum yields (ΦFL) and 1O2 yields. The study on the decay pathways indicates that such an anti‐heavy atom effect predominately stems from the lifetimes of the excited‐state species. The photodynamic mechanism study here will lead to more advanced FAP‐MG systems with high spatiotemporal resolution.
Third‐order super‐twisting control of a double stator asynchronous generator integrated in a wind turbine system under single‐phase open fault
Authors: Guettab Abdelkader , Bounadja Elhadj , Boudjema Zinelaabidine , Taleb Rachid
Published: December 2022

This paper deals with the control approach enhancement of a wind power generation system (WPGS) based on a double stator asynchronous generator (DSAG) under single‐phase open fault (SPOF). This type of machine, which collects the qualities of the squirrel cage asynchronous machine and these of the multiphase machine, has attracted the attention of several researchers, especially in the field of the wind energy. Classical sliding mode control (SMC) has been widely developed for the design of control systems. However, the use of SMC has several inconveniences such as the high chattering effect, large transient state error, and less robustness, which limit its utilization in practical applications. In order to improve the performance of the DSAG‐based WPGS, a third‐order super‐twisting controller (TOSTC) with chattering‐free is proposed. Then, an SPOF test is performed to prove the ability of the DSAG to work under degraded circumstances and guarantees to provide appropriate electrical energy to the grid without notable effects. The proposed system and its control under such conditions are illustrated by numerical simulations. The obtained results demonstrate the superior performance of the proposed system.
Effect of joints on microwave fracturing of the Bukit Timah granite using an open‐ended antenna
Authors: Ma Zhongjun , Zheng Yanlong , He Lei , Li Jianchun
Published: December 2022

Microwave fracturing of rocks before mechanical breakage could improve the performance of mechanical excavators and reduce environmental impacts. Previous research focused on the microwave fracturing of intact rock blocks. By using an open‐ended antenna, this paper investigates the effect of pre‐existing joints on the microwave fracturing of the Singapore Bukit Timah granite blocks. The results show that the specimens are weakened in the manners of cracking, spalling, melting, or a combination of them. The crack number and the total crack length produced by microwave treatment of jointed rock blocks are slightly smaller than those in the intact rock blocks. The interaction between joints and microwave‐induced cracks can be summarized into the following four patterns: (1) microwave‐induced cracks become arrested so that the crack propagation is terminated; (2) microwave‐induced cracks penetrate the joints and continue to propagate; (3) microwave‐induced cracks become deflected along the joints; and (4) microwave‐induced cracks propagate forward following the joints. The smaller the approach angle between the microwave‐induced crack and the pre‐existing joint is, the more microwave‐induced cracks tend to be arrested at the joint. Increasing the approach angle between the microwave‐induced crack and the joint can increase the chance of microwave‐induced crack penetrating the joint. The results also show that the smaller the distance is between the microwave radiation point and the joint, the easier it is for microwave‐induced cracks to penetrate the joints; otherwise, the microwave‐induced crack is more likely to be arrested at the pre‐existing joint.
Predictors of family‐based treatment for adolescent eating disorders: Do family or diagnostic factors matter?
Authors: Datta Nandini , Hagan Kelsey , Bohon Cara , Stern May , Kim Bohye , Matheson Brittany E. , Gorrell Sasha , Le Grange Daniel , Lock James D.
Published: December 2022

Objective

Misconceptions around which patients will and will not benefit from family‐based treatment (FBT) for adolescent eating disorders (EDs) limit referrals and access to this treatment modality. The present study explored whether common demographic and clinical factors that may prevent referral to FBT predict treatment outcomes in adolescent anorexia nervosa (AN) and bulimia nervosa (BN).

Method

The following predictors of treatment outcomes were assessed: baseline family and diagnostic factors (socioeconomic status, comorbidity, illness duration, parent feelings of self‐efficacy, family status, prior treatment, sex and prior hospitalizations) in a combined sample of adolescents receiving FBT compared to those randomized to other treatment conditions, across six clinical trials in the United States and Canada (total n = 724, ages 12–18, 90% female across both diagnoses). AN and BN samples were examined separately.

Results

Any prior ED treatment emerged as the only predictor of outcome in AN and BN, such that having no prior treatment predicted better outcomes in FBT for AN, and in both FBT and other treatment modalities for BN. No other sociodemographic or clinical variables predicted outcomes for AN or BN in FBT or in other evidence‐based treatment modalities.

Conclusions

The findings of this exploratory analysis suggest that commonly assumed factors do not predict outcome in FBT. Specifically socioeconomic and demographic factors or clinical variability in families seeking treatment do not predict treatment outcomes in FBT, or other evidence‐based treatment modalities, with the exception of prior treatment. Providers should consider referring to FBT even when these factors are present.

Public Significance

This manuscript reports that commonly assumed family, sociodemographic and diagnostic factors do not predict outcome in FBT or other evidence‐based treatment modalities, with the exception of prior treatment. This data may be helpful for providers when considering referrals to FBT in the context of variability in these variables.
Divergent Behavior in the Chemistry of Metal‐Bis(dithiolene) Complexes Appended with Peripheral Aliphatic Butyl Chains
Authors: Prignot Erwan , Zhang Chanjuan , Jeannin Olivier , Halime Zakaria , Gramage‐Doria Rafael , Camerel Franck
Published: December 2022

Metal‐bis(dithiolene) complexes derived from Ni(II), Co(II), Pd(II), Pt(II) and Au(III), bearing butyl aliphatic chains have been synthesized, and fully characterized by a variety of spectroscopic techniques including NMR, UV‐vis, IR, HRMS, CV, and X‐ray diffraction studies. This comparative study made possible to establish that the Co(II) species appear to be dimeric in the solid state as well as in solution. On the other hand, the coordination complexes based on Ni(II), Pd(II), Pt(II) and Au(III), feature a monomeric structure in both solution and solid state. These metal‐bis(dithiolene) complexes are remarkably stable in solution and, in stark contrast to precedents in the literature, they retain their square planar geometry even in presence of pyridine derivatives reported for their apical binding on metal‐bis(dithiolene) complexes.
Continuous Flow Chemistry Synthesis of Spirocyclic Sultams and Isoquinolines through Rhodium‐Catalyzed C−H Activation.
Authors: Zheng Ting , Lin Meng‐Ling , Dong Lin
Published: December 2022

In recent years, continuous flow technology have been applied to C−H activation to improve reaction efficiency. Herein, various imines and alkynes have been smoothly applied to continuous flow system. A series of spirocyclic sultams and isoquinolines can be obtained in excellent yields through [3+2] or [4+2] annulation reactions under relatively mild conditions.
One‐Pot Synthesis of 4‐Thiocyanato‐1H‐pyrazoles through Electrochemical Multicomponent Thiocyanation under Metal‐ and Oxidant‐Free Conditions
Authors: Zhang Ying , Xu Sen , Zhu Yutao , Xu Qingyu , Gao Huanjie , Liang Zeyao , Yao Xiaoquan
Published: December 2022

An electrochemical oxidative three‐component tandem reaction of arylhydrazines, 1,3‐diketones and ammonium thiocyanate has been established to construct 4‐thiocyanato‐1H‐pyrazoles under metal‐, oxidant‐free and mild conditions in an undivided cell. Various 4‐thiocyanato‐1H‐pyrazole derivatives could be obtained with broad substrate scope, and excellent functional group tolerance from available raw materials in moderate to excellent yields. This thiocyanation protocol with practicability and scalability features economical and eco‐friendly.
Pyridine‐Boryl Radical Mediated Decarboxylative Homolytic Substitution of N‐hydroxyphthalimide Ester with Ar2X2 (X=S, Se)
Authors: Cao Jia , Gao Liuzhou , Wang Guoqiang , Li Shuhua
Published: December 2022

Herein, we report a metal‐free approach to construct C−X (X=S, Se) bonds with the broadly available N‐hydroxyphthalimide esters and disulfides/diselenides (Ar2X2, X=S or Se) using bis(pinacolato)diboron as the reductant. Density functional theory calculations and control experiments reveal that such a C−X bond formation process is reductive decarboxylation mediated from pyridine‐boryl radical to yield alkyl or aryl radical. The resulting carbon radical then reacts with disulfides or diselenides via a bimolecular homolytic substitution (SH2) mechanism to afford the corresponding sulfides or selenides. This method displays a high functional group tolerance and broad substrate applicability.
Modulation of central pain mechanisms using high‐definition transcranial direct current stimulation: A double‐blind, sham‐controlled study
Authors: Kold Sebastian , Graven‐Nielsen Thomas
Published: December 2022

Background

The use of high‐definition transcranial direct current stimulation (HD‐tDCS) has shown analgesic effects in some chronic pain patients, but limited anti‐nociceptive effects in healthy asymptomatic subjects.

Methods

This double‐blinded sham‐controlled study assessed the effects of HD‐tDCS applied on three consecutive days on central pain mechanisms in healthy participants with (N = 40) and without (N = 40) prolonged experimental pain induced by intramuscular injection of nerve growth factor into the right hand on Day 1. Participants were randomly assigned to Sham‐tDCS (N = 20 with pain, N = 20 without) or Active‐tDCS (N = 20 with pain, N = 20 without) targeting simultaneously the primary motor cortex and dorsolateral prefrontal cortex for 20 min with 2 mA stimulation intensity. Central pain mechanisms were assessed by cuff algometry on the legs measuring pressure pain sensitivity, temporal summation of pain (TSP) and conditioned pain modulation (CPM), at baseline and after HD‐tDCS on Day 2 and Day 3. Based on subject's assessment of received HD‐tDCS (sham or active), they were effectively blinded.

Results

Compared with Sham‐tDCS, Active‐tDCS did not significantly reduce the average NGF‐induced pain intensity. Tonic pain‐induced temporal summation at Day 2 and Day 3 was significantly lower in the NGF‐pain group under Active‐tDCS compared to the pain group with Sham‐tDCS (p ≤ 0.05). No significant differences were found in the cuff pressure pain detection/tolerance thresholds or CPM effect across the 3 days of HD‐tDCS in any of the four groups.

Conclusion

HD‐tDCS reduced the facilitation of TSP caused by tonic pain suggesting that efficacy of HD‐tDCS might depend on the presence of sensitized central pain mechanisms.
State of the art of augmented reality capabilities for civil infrastructure applications
Authors: Xu Jiaqi , Doyle Derek , Moreu Fernando
Published: December 2022

Augmented reality (AR) is a technology superimposes interactional virtual objects onto a real environment. Since the beginning of the millennium, AR technologies have rapidly grown, with significant research publications in engineering and science. However, the civil infrastructure community has minimally implemented AR technologies to date. Civil engineers face one of the challenges when understanding and using AR is the lack of a classification of AR in the context of capabilities for civil infrastructure applications. Like most engineering fields, practitioners in civil infrastructure prioritize understanding a new technology's maturity level before considering its adoption and field implementation. This article compares the capabilities of 16 AR head‐mounted devices (HMDs) available in the market since 2017, ranking them in terms of performance for civil infrastructure implementations. Finally, the authors recommend a development framework for functional AR interfaces with civil infrastructure and operations.
Rational engineering of metal–organic coordination networks into facet‐controlled phosphides for overall water splitting
Authors: Yilmaz Gamze , Yang Tong , Lim Kane Jian Hong , Chee See Wee , Shen Lei , Mirsaidov Utkur , Bosman Michel , Ho Ghim Wei
Published: December 2022

Although transition metal phosphide electrocatalysts display unique electronic structure that serves as functional centers for hydrogen evolution reaction, the synthesis of this class of materials for oxygen evolution remains a challenge due to the complex multielectron transfer pathways and sluggish reaction kinetics. This study details an in‐situ modification and transformation of cyanide‐bridged nickel‐iron (CN‐NiFe) organometallic hybrid into the preferential Fe2P phase with prevailing exposed faceted active centers by leveraging on the facile coordinate cleavage dynamics and compound reactivity of labile metal organic coordination frameworks. The resultant transition metal phosphide attains high electrochemical surface area, low Tafel slope, and low overpotential for the oxygen evolution reaction, while also demonstrating bifunctional electrocatalytic performance for overall water splitting. Comprehensive experimental studies and density functional theory calculations reveal that the exceptional catalytic activity originates from the transformation of framework metallic sites into preferential active sites allows an optimal adsorption of oxygen evolution reaction intermediates.

image