bluuebunny/crossref_metadata_2025 huggingface dataset:
Alkyne Insertion Enabled Vinyl to Acyl 1,5‐Palladium Migration: Rapid Access to Substituted 5‐Membered‐Dihydrobenzofurans and Indolines
Authors: Ding Mingruo , Ou Pengcheng , Li Xuening , Yu Yinghua , Niu Mengmeng , Yang Yongjian , Huang Yewei , Wang Zhi‐Xiang , Huang Xueliang
Published: February 2023

“Through space” palladium/hydrogen shift is an efficient strategy to achieve selective functionalization of a specific remote C−H bond. Compared with relatively extensive exploited 1,4‐palladium migration process, the relevant 1,5‐Pd/H shift was far less investigated. We herein report a novel 1,5‐Pd/H shift pattern between a vinyl and an acyl group. Through the pattern, rapid access to 5‐membered‐dihydrobenzofuran and indoline derivatives has been achieved. Further studies have unveiled an unprecedented trifunctionalization (vinylation, alkynylation and amination) of a phenyl ring through 1,5‐palladium migration relayed decarbonylative Catellani type reaction. A series of mechanistic investigations and DFT calculations have provided insights into the reaction pathway. Notably, it was unveiled that the 1,5‐palladium migration in our case prefers a stepwise mechanism involving a PdIVintermediate.
Electrically Switchable Persistent Spin Texture in a Two‐Dimensional Hybrid Perovskite Ferroelectric
Authors: Guo Wuqian , Xu Haojie , Ma Yu , Liu Yi , Gao Heng , Hu Tao , Ren Wei , Luo Junhua , Sun Zhihua
Published: February 2023

As a momentum‐independent spin configuration, persistent spin texture (PST) could avoid spin relaxation and play an advantageous role in spin lifetime. Nevertheless, manipulation of PST is a challenge due to the limited materials and ambiguous structure–property relationships. Herein, we present electrically switchable PST in a new 2D perovskite ferroelectric, (PA)2CsPb2Br7 (where PA is n‐pentylammonium), which has a high Curie temperature of 349 K, evident spontaneous polarization (3.2 μC cm−2) and a low coercive electric field of 5.3 kV cm−1. The combination of symmetry‐breaking in ferroelectrics and effective spin‐orbit field facilitates intrinsic PST in the bulk and monolayer structure models. Strikingly, the directions of spin texture are reversible by switching the spontaneous electric polarization. This electric switching behavior relates to the tilting of PbBr6 octahedra and the reorientation of organic PA+ cations. Our studies on ferroelectric PST of 2D hybrid perovskites afford a platform for electrical spin texture manipulation.
Immunogenic Cell Death Inducing Metal Complexes for Cancer Therapy
Authors: Zhang Lingpu , Montesdeoca Nicolás , Karges Johannes , Xiao Haihua
Published: February 2023

Cancer is one of the deadliest diseases worldwide. Recent statistics have shown that metastases and tumor relapse are the leading causes of cancer‐associated deaths. While traditional treatments are able to efficiently remove the primary tumor, secondary tumors remain poorly accessible. Capitalizing on this there is an urgent need for novel treatment modalities. Among the most promising approaches, increasing research interest has been devoted to immunogenic cell death inducing agents that are able to trigger localized cell death of the cancer cells as well as induce an immune response inside the whole organism. Preliminary studies have shown that immunogenic cell death inducing compounds could be able to overcome metastatic and relapsing tumors. Herein, the application of metal complexes as immunogenic cell death inducing compounds is systematically reviewed.
How to make a vampire
Authors: Smith Timothy D. , Prufrock Kristen A. , DeLeon Valerie B.
Published: February 2023

Herein, we compared the developmental maturity of the cranium, limbs, and feeding apparatus in a perinatal common vampire bat relative to its mother. In addition, we introduce a method for combining two computed tomographic imaging techniques to three‐dimensionally reconstruct endocasts in poorly ossified crania. The Desmodus specimens were scanned using microcomputed tomography (microCT) and diffusible iodine‐based contrast‐enhanced CT to image bone and soft tissues. Muscles of the jaw and limbs, and the endocranial cavity were segmented using imaging software. Endocranial volume (ECV) of the perinatal Desmodus is 74% of adult ECV. The facial skeletal is less developed (e.g., palatal length 60% of adult length), but volumes for alveolar crypts/sockets of permanent teeth are nearly identical. The forelimb skeleton is uniformly less ossified than the distal hind limb, with no secondary centers ossified and an entirely cartilaginous carpus. All epiphyseal growth zones are active in the brachium and antebrachium, with the distal radius exhibiting the greatest number of proliferating chondrocytes arranged in columns. The hind limb skeleton is precociously ossified from the knee distally. The musculature of the fore limb, temporalis, and masseter muscles appear weakly developed (6–11% of the adult volume). In contrast, the leg and foot musculature is better developed (23–25% of adult volume), possibly enhancing the newborn's capability to grip the mother's fur. Desmodus is born relatively large, and our results suggest they are born neurally and dentally precocious, with generally underdeveloped limbs, especially the fore limb.
Long‐life high‐capacity lithium battery with liquid organic cathode and sulfide solid electrolyte
Authors: Peng Jian , Wu Dengxu , Li Hong , Chen Liquan , Wu Fan
Published: February 2023

Electrochemical batteries with organic electrode materials have attracted worldwide attention due to their high safety, low cost, renewability, low contamination, and easiness of recycling. However, the practical application of such system is limited by low density, low electronic/ionic conductivity, and the dissolution of organic electrode materials in conventional liquid electrolytes. Herein, a novel battery configuration is proposed to replace liquid electrolyte/solid organic cathode with solid electrolyte/liquid organic cathode to ultimately solve the shuttle effect and dissolution problem of organic cathodes. More importantly, this configuration combines room‐temperature high‐safety liquid lithium metal anode Li‐BP‐DME that can essentially inhibit lithium dendrite nucleation/growth and sulfide SE with ultrahigh room‐temperature ionic conductivity for facilitated ion‐conduction.
Standard versus low‐dose nab‐paclitaxel in previously treated patients with advanced non‐small cell lung cancer: A randomized phase II trial (JMTO LC14‐01)
Authors: Takeuchi Susumu , Kubota Kaoru , Sugawara Shunichi , Teramukai Satoshi , Noro Rintaro , Fujikawa Kei , Hirose Takashi , Atagi Shinji , Minami Seigo , Iida Shinichiro , Kuraishi Hiroshi , Aiba Tomoiki , Minegishi Yuji , Matsumoto Masaru , Seike Masahiro , Gemma Akihiko , Kawahara Masaaki ,   Japan‐Multinational Trial Organization (JMTO)
Published: February 2023

Background

Nab‐paclitaxel (nab‐PTX) has better transfer to tumor tissue than cremophor‐based paclitaxel. It suggests that the optimum dose of nab‐PTX might be lower than the dose and schedule that is widely used. We designed a randomized phase II trial to examine the clinical utility and safety of nab‐PTX in patients with previously treated advanced non‐small cell lung cancer (NSCLC).

Methods

Patients were randomly allocated (1:1) to receive nab‐PTX monotherapy at 100 mg/m2 (group A) or 70 mg/m2 (group B). The primary endpoint was progression‐free survival (PFS). Secondary endpoints included overall survival (OS), objective response rate (ORR), and adverse events (AEs).

Results

Finally, 81 patients were randomized. Similar results were observed in both groups for PFS (3.75 vs. 3.71 months), OS (13.50 vs. 16.13 months), or ORR (20.5% vs. 23.1%). The incidences of grade 3 or worse AEs were 57.5% in group A and 41.5% in group B. The proportion of serious side effects was 10.0% in group A and 4.9% in group B.

Conclusion

Both standard dose and low dose of nab‐PTX monotherapy are active for previously treated NSCLC patients with better safety profile. Therefore, nab‐PTX 70 mg/m2 dose and schedule in the trial would be a reasonable option.
Long‐term follow‐up results of pediatric and adolescent patients with localized Ewing sarcoma treated based on stratified modalities
Authors: Zeng Chenggong , Chen Tingting , Wang Juan , Sun Feifei , Huang Junting , Lu Suying , Zhu Jia , Zhang Yizhuo , Sun Xiaofei , Zhen Zijun
Published: February 2023

Background

Compared with other pediatric tumors, little advances were achieved in studies on the stratified treatment in localized Ewing sarcoma. Most pediatric oncology groups treated Ewing sarcoma according to whether there was an existing metastasis, without involving more prognostic factors. In this study, patients with localized Ewing sarcoma were divided into resectable and unresectable groups at diagnosis and received chemotherapy with different intensity, for the purpose of achieving good efficacy, avoiding overtreatment and reducing unnecessary toxicity.

Methods

A total of 143 patients with a median age of 10 years old diagnosed with localized Ewing sarcoma in this retrospective study were divided into two cohorts (Cohort 1, n = 42; Cohort 2, n = 101) and patients in Cohort 2 received chemotherapy with different intensity (Regimen 1, n = 52; Regimen 2, n = 49). Outcomes were analyzed using the Kaplan–Meier method to estimate event‐free survival (EFS) and overall survival (OS), and the curves were compared using the log‐rank test.

Results

The 5‐year EFS and 5‐year OS for all the patients were 69.0% and 77.5%. The 5‐year EFS for Cohort 1 and Cohort 2 were 76.0% and 66.1% (p = 0.31), and the 5‐year OS were 83.0% and 75.1% (p = 0.30), respectively. In Cohort 2, the 5‐year EFS rate of patients treated with Regimen 2 was significantly higher than that of patients treated with Regimen 1 (74.5% vs. 58.3%, p = 0.03).

Conclusions

According to whether a grossly complete resection was received at the time of diagnosis, localized Ewing sarcoma patients in this study were stratified into two groups and received different intensities of chemotherapy, which achieved good efficacy and avoided overtreatment and reduced unnecessary toxicity.
Association between immune checkpoint inhibitors and myocardial infarction in Asians: A population‐based self‐controlled case series
Authors: Chan Jeffrey Shi Kai , Tang Pias , Lee Teddy Tai Loy , Chou Oscar Hou In , Lee Yan Hiu Athena , Li Guoliang , Leung Fung Ping , Wong Wing Tak , Liu Tong , Tse Gary
Published: February 2023

Background

While immune checkpoint inhibitors (ICIs) are associated with elevated cardiovascular risks, evidence of any association between ICIs and myocardial infarction (MI) was scarce, especially in Asians.

Methods

Using prospectively collected population‐based data, this self‐controlled case series included patients prescribed an ICI between 1/1/2014 and 31/12/2020 in Hong Kong who had MI within January 1, 2013 to December 31, 2021. Incidence rate ratios (IRRs) for MI during and after ICI exposure were estimated, compared to the year before ICI initiation.

Results

Of 3684 identified ICI users, 24 had MI during the study period. MI incidence increased significantly in the first 90 days of exposure (IRR 3.59 [95% confidence interval: 1.31–9.83], p = 0.013), but not days 91–180 (p = 0.148) or ≥181 (p = 0.591) of exposure, nor postexposure (p = 0.923). Sensitivity analyses excluding patients with MI‐related death and incorporating extended exposure periods produced consistent results separately.

Conclusions

ICIs were associated with increased MI incidence in Asian Chinese patients during the first 90 days of use, but not later.
Value co‐creation and customer retention in services: Identifying a relevant moderator and mediator
Authors: Banik Shanta , Rabbanee Fazlul K.
Published: February 2023

This research explores the effects of the DART model of value co‐creation on customer retention. To do so, the current research examines the moderating role of types of customer (i.e., corporate vs. retail) and the mediating effect of customer engagement. Two studies were conducted through structured surveys among 362 bank customers (Study 1) and 316 hotel customers (Study 2). Partial least‐squares‐based structural equation modeling (PLS‐SEM) was employed to analyze the data. The results of Study 1 show that each element of the DART model significantly influences customer retention. The effects of dialog, risk assessment, and transparency on customer retention are found to be higher (lower) for corporate (retail) customers, while the effect of access on customer retention is higher (lower) for retail (corporate) customers. Study 2 further identified customer engagement as a mediator explaining the underlying mechanism in the links between each element of the DART model and customer retention. Theoretical contributions and managerial implications of the findings are discussed.
Controlling Activity of Heterogeneous Cu Single‐Atom Catalysts by Fine‐Tuning the Redox Properties of CeO2‐TiO2 Supports
Authors: Abdel‐Mageed Ali M. , Cisneros Sebastian , Mosrati Jawaher , Atia Hanan , Vuong Thanh Huyen , Rockstroh Nils , Wohlrab Sebastian , Brückner Angelika , Rabeah Jabor
Published: February 2023

Understanding and enhancing the activity of heterogeneous single‐atom catalysts (SACs) are indispensable aspects to use them in industrial applications. Among these, low‐temperature CO oxidation is considered as a model reaction for testing a wide‐range of oxidation catalysts, and as an essential process for the exhaust aftertreatment in modern combustion engines. This study demonstrates that the activity of heterogeneous Cu/CeO2−TiO2 SAC catalysts can be fine‐tuned by controlling the Ce/Ti ratio in CeO2−TiO2 supports, with the highest catalytic activity achieved for a Ce/Ti molar ratio of 0.18. Based on DRIFT, EEL, and EPR spectroscopies, together with high‐resolution electron microscopy and H2‐TPR measurements, it is inferred that the optimized Ce/Ti ratio correlates with i) highest dispersion of separate CeO2 particles on TiO2 surface, ii) more facile reduction of Ce4+ to Ce3+, and iii) enhanced formation of −Cu2+−O−Ce4+−⇆−Cu+−□−Ce3+− redox shuttles, which play a dual role for CO adsorption and O2‐activation. These results extend the understanding of heterogeneous metal single‐atom catalysts and constitute a robust approach for the rational control of their catalytic performance in technically relevant applications.
Associations between diagnosis with stroke, comorbidities, and activity of daily living among older adults in the United States
Authors: Ruksakulpiwat Suebsarn , Zhou Wendie , Phianhasin Lalipat , Benjasirisan Chitchanok , Salehizadeh Saeideh , Wang Limin , Voss Joachim G.
Published: February 2023

Background

Stroke is the leading cause of mortality. This study aimed to investigate the association between stroke, comorbidities, and activity of daily living (ADL) among older adults in the United States.

Methods

Participants were 1165 older adults aged 60 and older from two waves (2016 and 2018) of the Health and Retirement Study who had a stroke. Descriptive statistics were used to describe demographic information and comorbidities. Logistic regressions and multiple regression analyses were used to determine associations between stroke, comorbidities, and ADL.

Results

The mean age was 75.32 ± 9.5 years, and 55.6% were female. An adjusted analysis shows that older stroke adults living with diabetes as comorbidity are significantly associated with difficulty in dressing, walking, bedding, and toileting. Moreover, depression was significantly associated with difficulty in dressing, walking, bathing, eating, and bedding. At the same time, heart conditions and hypertension as comorbidity were rarely associated with difficulty in ADL. After adjusting for age and sex, heart condition and depression are significantly associated with seeing a doctor for stroke (odds ratio [OR]: 0.66; 95% confidence interval [CI]: 0.49–0.91; p = 0.01) and stroke therapy (OR: 0.46; 95% CI: 0.25–0.84; p = 0.01). Finally, stroke problem (unstandardized β [B] = 0.58, p = 0.017) and stroke therapy (B = 1.42, p < 0.001) significantly predict a lower level of independence.

Conclusion

This study could benefit healthcare professionals in developing further interventions to improve older stroke adults' lives, especially those with a high level of dependence.
Single‐Site Molecular Ruthenium(II) Water‐Oxidation Catalysts Grafted into a Polymer‐Modified Surface for Improved Stability and Efficiency
Authors: Badiei Yosra M. , Annon Oshane , Maldonado Christina , Delgado Emily , Nguyen Caroline , Rivera Christina , Li Clive , Ortega Abril Flores
Published: February 2023

Water‐oxidation is a mechanistic bottleneck in artificial photosynthesis that is critical for achieving sustainable energy‐to‐fuel conversion. Grafting molecular water‐oxidation catalyst assemblies on the surface of a polymer can engender better stability and higher efficiency. Herein, we present a hybrid construct which consists of a molecular single‐site RuCat1 encapsulated into a UV cross‐linked polymer assembly on an F‐doped tin oxide (FTO). Incorporation of high‐density surface‐binding sites (COO− groups) resulted in a high surface loading of the RuCat1 and surface stability as shown from ATR‐FTIR, UV‐vis and cyclic voltammetry data. Furthermore, we found that the grafted RuCat1 into the polymer brush layers promotes pH‐dependent electrocatalytic water‐oxidation with a turnover frequency of 0.45 s−1 and an estimated 88 % faradaic efficiency during control potential electrolysis at pH 8.5. The general applicability of this approach is illustrated by screening a series of molecular single‐site catalysts which points to the importance of electrostatic interactions as well as hydrogen bonding in the functionalization of the electrode.
Facile construction of a multilayered interface for a durable lithium‐rich cathode
Authors: Xu Zhou , Yuan Yifei , Tang Qing , Nie Xiangkun , Li Jianwei , Sun Qing , Ci Naixuan , Xi Zhenjie , Han Guifang , Ci Lijie , Min Guanghui
Published: February 2023

Layered lithium‐rich manganese‐based oxide (LRMO) has the limitation of inevitable evolution of lattice oxygen release and layered structure transformation. Herein, a multilayer reconstruction strategy is applied to LRMO via facile pyrolysis of potassium Prussian blue. The multilayer interface is visually observed using an atomic‐resolution scanning transmission electron microscope and a high‐resolution transmission electron microscope. Combined with the electrochemical characterization, the redox of lattice oxygen is suppressed during the initial charging. In situ X‐ray diffraction and the high‐resolution transmission electron microscope demonstrate that the suppressed evolution of lattice oxygen eliminates the variation in the unit cell parameters during initial (de)lithiation, which further prevents lattice distortion during long cycling. As a result, the initial Coulombic efficiency of the modified LRMO is up to 87.31%, and the rate capacity and long‐term cycle stability also improved considerably. In this work, a facile surface reconstruction strategy is used to suppress vigorous anionic redox, which is expected to stimulate material design in high‐performance lithium ion batteries.
Boosting the Ni–Zn interplay via O/N dual coordination for high‐efficiency CO2 electroreduction
Authors: Zhang Ying , Jiang Hailei , Kumar Anuj , Zhang Hongchuan , Li Zongge , Xu Tongxin , Pan Yuan , Wang Yaqun , Liu Zhiming , Zhang Guoxin , Yan Zifeng
Published: February 2023

Design of supportive atomic sites with a controllably adjusted coordinating environment is essential to advancing the reduction of CO2 to value‐added fuels and chemicals and to achieving carbon neutralization. Herein, atomic Ni (Zn) sites that are uniquely coordinated with ternary Zn (Ni)/N/O ligands were successfully decorated on formamide‐derived porous carbon nanomaterials, possibly forming an atomic structure of Ni(N2O1)‐Zn(N2O1), as studied by combining X‐ray photoelectron spectroscopy and X‐ray absorption spectroscopy. With the mediation of additional O coordination, the Ni–Zn dual site induces significantly decreased desorption of molecular CO. The NiZn‐NC decorated with rich Ni(N2O1)‐Zn(N2O1) sites remarkably gained >97% CO Faraday efficiency over a wide potential range of ‒0.8 to ‒1.1 V (relative to reversible hydrogen electrode). Density functional theory computations suggest that the N/O dual coordination effectively modulates the electronic structure of the Ni–Zn duplex and optimizes the adsorption and conversion properties of CO2 and subsequent intermediates. Different from the conventional pathway of using Ni as the active site in the Ni–Zn duplex, it is found that the Ni‐neighboring Zn sites in the Ni(N2O1)‐Zn(N2O1) coordination showed much lower energy barriers of the CO2 protonation step and the subsequent dehydroxylation step.
Thermally Activated Delayed Fluorescence and Room‐Temperature Phosphorescence in Materials with Imidazo‐pyrazine‐5,6‐dicarbonitrile Acceptors
Authors: Xu Pengfei , Hojo Ryoga , Hudson Zachary M.
Published: February 2023

Three donor‐acceptor compounds based on the imidazo‐pyrazine‐5,6‐dicarbonitrile (IPDC) acceptor were synthesized. The IPDC emitters exhibit blue to near‐infrared (NIR) emission with up to 54 % photoluminescent quantum yield. 9,9‐Dimethyl‐9,10‐dihydroacridine (ACR), phenoxazine (POX), and phenothiazine (PTZ) served as electron donors. IPDC‐POX displayed NIR emission in toluene solution, while showing room‐temperature phosphorescence in the solid state. IPDC‐ACR exhibited yellow thermally activated delayed fluorescence. Interestingly, dual‐emissive behavior as well as excitation‐dependent thermally activated delayed fluorescence (TADF) was found for IPDC‐PTZ, arising from the two conformers of phenothiazine derivatives. Overall, this work describes a novel strong electron acceptor from the fusion of imidazole, pyrazine, and nitrile functional groups into one conjugated heterocycle for materials exhibiting NIR emission, TADF, and/or room‐temperature phosphorescence (RTP).
Toward a Comprehensive Understanding of Amorphous Photocatalysts: Fundamental Hypotheses and Applications in CO2 Photoreduction
Authors: Powar Niket S. , Kim Dongyun , In Su‐Il
Published: February 2023

In principle, photocatalytic activity can be precisely controlled with crystalline catalysts. However, an amorphous photocatalyst could be a viable candidate for CO2 photoreduction to form value‐added products. The amorphous phase is currently part of the crystalline material in several ongoing CO2 photoreduction studies. Additionally, no study indicates the amorphous material required for overall CO2 photoreduction. This perspective review article highlights fundamental assumptions that are necessary to gain insights and understand the effectiveness of amorphous photocatalysts for CO2 photoreduction. We start with basic ideas and theories about these materials, including light harvesting, variable coordination number, and the interaction of CO2 molecules with the amorphous catalytic surface. To understand the prospects of the amorphous photocatalyst, we explore machine learning with EXAFS. Furthermore, we discuss product selectivity and regeneration of photocatalysts in detail. Finally, we briefly review the work in progress on amorphous materials and compare it to that on crystalline ones.
Structural Engineering of Red Luminogens to Realize High Emission Efficiency through ACQ‐to‐AIE Transformation
Authors: Sun Hua , He Tengfei , Zhang Chuchen , Wang Shifan , Dong Liming , Li Zhao , Gu Pei‐Yang , Wang Zhe , Long Guankui , Zhang Qichun
Published: February 2023

Deep red/near‐infrared (NIR, >650 nm) emissive organic luminophores with aggregation‐induced emission (AIE) behaviours have emerged as promising candidates for applications in optoelectronic devices and biological fields. However, the molecular design philosophy for AIE luminogens (AIEgens) with narrow band gaps are rarely explored. Herein, we rationally designed two red organic luminophores, FITPA and FIMPA, by considering the enlargement of transition dipole moment in the charge‐transfer state and the transformation from aggregation‐caused quenching (ACQ) to AIE. The transition dipole moments were effectively enhanced with a “V‐shaped” molecular configuration. Meanwhile, the ACQ‐to‐AIE transformation from FITPA to FIMPA was induced by a methoxy‐substitution strategy. The experimental and theoretical results demonstrated that the ACQ‐to‐AIE transformation originated from a crystallization‐induced emission (CIE) effect because of additional weak interactions in the aggregate state introduced by methoxy groups. Owing to the enhanced transition dipole moment and AIE behaviour, FIMPA presented intense luminescence covering the red‐to‐NIR region, with a photoluminescence quantum yield (PLQY) of up to 38 % in solid state. The promising cell‐imaging performance further verified the great potential of FIMPA in biological applications. These results provide a guideline for the development of red and NIR AIEgens through comprehensive consideration of both the effect of molecular structure and molecular interactions in aggregate states.
Nanolobatone A, An Unprecedented Diterpenoid and Related New Casbanoids from the Hainan Soft Coral Sinularia nanolobata
Authors: Liu Jiao , Li Song‐Wei , Zhao Qing‐Min , Zhang Zai‐Yong , Yao Li‐Gong , Gu Yu‐Cheng , Lan Le‐Fu , Guo Yue‐Wei
Published: February 2023

Nanolobatone A, featuring an unprecedented tricyclo[10.3.0.01,2]pentadecane carbon skeleton, along with four new polyoxygenated and four unusual endoperoxide‐bridged casbane‐type diterpenoids were isolated from the Hainan soft coral Sinularia nanolobata. The structures of the new compounds were established by extensive spectroscopic analysis, X‐ray diffraction analysis, and time‐dependent density functional theory/electronic circular dichroism calculations. A plausible biosynthetic pathway of new isolates was proposed. Bioassays revealed that nanolobatone A showed weak antibacterial activity against the Gram‐positive bacteria Streptococcus pyogenes.
A New Type of Valence Tautomerism in Cobalt Dioxolene Complexes – Temperature‐Induced Transition from a Cobalt(III) Catecholate to a Low‐Spin Cobalt(II) Semiquinonate State
Authors: Metzger Christoph , Dolai Ramapada , Reh Sabine , Kelm Harald , Schmitz Markus , Oelkers Benjamin , Sawall Mathias , Neymeyr Klaus , Krüger Hans‐Jörg
Published: February 2023

The synthesis and characterization of the monocationic cobalt(III) catecholate complex [Co(L‐N4tBu2)(Cl2cat)]+ (L‐N4tBu2=N,N’‐Di‐tert.‐butyl‐2,11‐diaza[3.3](2,6)pyridinophane, Cl2cat2−=4,5‐dichlorocatecholate) are presented. The complex exhibits valence tautomeric properties in solution; but, in contrast to the usually observed conversion from a cobalt(III) catecholate to a high‐spin cobalt(II) semiquinonate state, valence tautomerism of [Co(L‐N4tBu2)(Cl2cat)]+ leads to the formation of a low‐spin cobalt(II) semiquinonate complex upon raising the temperature. This new type of valence tautomerism for a cobalt dioxolene complex has been unambiguously established by a detailed spectroscopic investigation using variable‐temperature NMR, IR and UV‐Vis‐NIR spectroscopy. Determination of the enthalpies and entropies characterizing the valence tautomeric equilibria in various solutions shows that the influence of the solvent is almost exclusively entropic.
Comprehensive Investigation of Anion Species in Crystalline Li+ ion Conductor Li27−x[P4O7+xN9−x]O3 (x≈1.9(3))
Authors: Schneider Stefanie , Wendinger Eva‐Maria , Baran Volodymyr , Hatz Anna‐Katharina , Lotsch Bettina V. , Nentwig Markus , Oeckler Oliver , Bräuniger Thomas , Schnick Wolfgang
Published: February 2023

The Li+ ion conductor Li27−x[P4O7+xN9−x]O3 (x≈1.9) has been synthesized from P3N5, Li3N and Li2O in a Ta ampoule at 800 °C under Ar atmosphere. The cubic compound crystallizes in space group
with a=12.0106(14) Å and Z=4. It contains both non‐condensed [PO2N2]5− and [PO3N]4− tetrahedra as well as O2− ions, surrounded by Li+ ions. Charge neutrality is achieved by partial occupancy of Li positions, which was refined with neutron powder diffraction data. Measurements of the partial ionic and electronic conductivity show a total ionic conductivity of 6.6×10−8 S cm−1 with an activation energy of 0.46±0.02 eV and a bulk ionic conductivity of 4×10−6 S cm−1 at 25 °C, which is close to the ionic conductivity of amorphous lithium nitridophosphate. This makes Li27−x[P4O7+xN9−x]O3 an interesting candidate for investigation of structural factors affecting ionic conductivity in lithium oxonitridophosphates.
HighlyE‐Selective Olefin Synthesis Catalysed by Novel Quinoxalinone Photocatalyst under Visible Light Conditions
Authors: Xu Xin , Huang Jie , Gao Dandan , Wang Jiahua , Tang Xiang‐Ying , Wang Long
Published: February 2023

In photo‐induced olefin synthesis, the photocatalysts with high triplet energy could cause the isomerization of olefins. This study demonstrates a new quinoxalinone photocatalytic system for highly stereoselective alkenes preparation from alkenyl sulfones and alkyl boronic acids. Our photocatalyst could not convert the thermodynamically favoredE‐olefin toZ‐olefin, guaranteeing the highE‐configuration selectivity of the reaction. There is weak interaction between boronic acids and quinoxalinone according to NMR experiments, probably decreasing the oxidation potential of boronic acids. This system can be further extended to the allyl and alkynyl sulfones to give corresponding alkenes and alkynes.
Impact of the ultra‐long 48 mm drug‐eluting stent on procedural and clinical outcomes in patients with diffuse long coronary artery disease
Authors: Youn Young Jin , Jeon Ho Sung , Kim Young In , Lee Jung‐Hee , Park Young Jun , Cho Dong‐Hyuk , Son Jung‐Woo , Lee Jun‐Won , Ahn Min‐Soo , Ahn Sung Gyun , Kim Jang‐Young , Yoo Byung‐Su , Lee Seung‐Hwan , Yoon Junghan
Published: February 2023

Background

Diffuse coronary artery disease (CAD) is a prognostic factor after percutaneous coronary intervention (PCI) and requires multiple overlapping stent implantations.

Hypothesis

We investigated the impact of ultra‐long 48 mm drug‐eluting stent (DES) on procedural and clinical outcomes in real‐world practice.

Methods

Patients who underwent DES implantation for a lesion length of >40 mm were selected from a prospective registry between 2019 and 2021. Patients treated with one or more ultra‐long 48 mm DES were in the ultra‐long DES group (n = 221). The others comprised the conventional DES group (n = 428). Procedural and clinical outcomes were compared after propensity score matching (PSM). The primary endpoint was a device‐oriented composite outcome (DOCO) consisting of cardiac death, target vessel‐related myocardial infarction, and target lesion revascularization at 1‐year follow‐up.

Results

After PSM, 158 matched pairs of patients showed no differences in the baseline clinical and angiographic characteristics. The stent delivery failure rate, the use of guide‐extension catheter or anchor balloon technique, and the procedural success rate were similar for both groups. Approximately two‐thirds of lesions could be treated with one DES in the ultra‐long DES group. At 1‐year follow‐up, the DOCO was similar for both groups (2.5% vs. 0.6%,p = .168).

Conclusions

In daily clinical practice, ultra‐long DES implantation is as safe and effective as multiple overlapping conventional DES implants in treating diffuse long CAD. However, ultra‐long DES can reduce the number of stents. (Trial Registration: ClinicalTrials.gov Identifier: NCT02038127).
Develop medium‐ to long‐term climate information services to enhance comprehensive climate risk management in Africa
Authors: Omukuti Jessica , Wanzala Maureen Anyango , Ngaina Joshua , Ganola Phoebe
Published: February 2023

Increasing climate change risks in Africa, emerging from global warming and their interaction with non‐climate risks such as market, have increased the need for comprehensive Climate Risk Management (CRM) that considers both climatic and non‐climatic risks and enables actions that address the underlying drivers of vulnerability to these risks. However, comprehensive CRM requires holistic Climate Information Services (CIS), that is, CIS that balances between components focused on provision of short‐ and long‐term climate information for both local and non‐local decision makers. In this article, we ask: to what extent is CIS in Africa holistic? We review recent and ongoing CIS interventions in Africa to determine whether a balance of components between short‐ and long‐term CIS for local and non‐local decision makers is achieved for holistic CIS. We find a focus on provision of short‐term, that is, Sub‐Seasonal‐to‐Seasonal (S2S) CIS for local and non‐local decision makers, with limited focus on medium‐ to long‐term (MLT) CIS, particularly MLT CIS for local decision makers which represents the biggest gap to achieving holistic CIS in Africa. We present a supported case that ensuring holistic CIS in Africa will require a portfolio‐based approach to CIS development, particularly focusing on MLT CIS for local decision makers. We further highlight the need for integration of this MLT CIS for local decision makers into existing CIS. Achieving this will require: (a) experimentation and innovation with different CIS formats, products and timeframes to enable learning and flexibility to achieve desired goals; (b) capacity development of producers and consumers of climate information to ensure that they have the skills and expertise to understand and generate, and articulate needs and consume MLT CIS respectively; and (c) coordinated allocation of financial resources to ensure that all components of the holistic CIS are advanced.
At the border: A call to action for health equity for children with leukemia
Authors: Aristizabal Paula , Thornburg Courtney D. , Young Janine
Published: February 2023

The authors invite public health policy makers to be cognizant of the importance of where persons reside and consider focusing efforts to improve cancer outcomes in rural areas with concentrated poverty. They call for the attention of public health leaders and health care providers in both the United States and Mexico to mitigate the health disparities suffered by immigrants, a population that plays a vital role for the economies and social fabric of these two countries.
Weak Interactions Initiate C−H and C−C Bond Dissociation of Ethane on Nbn+ Clusters
Authors: Gan Wen , Huang Benben , Cui Chaonan , Hansen Klavs , Luo Zhixun
Published: February 2023

The conversion of ethane into value‐added chemicals under ambient conditions has attracted much attention but the mechanisms remain not fully understood. Here we report a study on the reaction of ethane with thermalized Nbn+ clusters based on a multiple‐ion laminar flow tube reactor combined with a triple quadrupole mass spectrometer (MIFT‐TQMS). It is found that ethane reacts with Nbn+ clusters to form both products of dehydrogenation and methane‐removal (odd‐carbon products). Combined with density functional theory (DFT) calculations, we studied the reaction mechanisms of the C−C bond activation and C−H bond cleavage on the Nbn+ clusters. It is unveiled that hydrogen atom transfer (HAT) initiates the reaction process, giving rise to the formation of Nb−C bonds and an elongated C−C distance in the HNbn+CH2CH3 motif. Subsequent reactions allow for C−C bond activation and a competitive HAT process which is associated with CH4 removal or H2 release, resulting in the production of the observed carbides.
Time‐resolved, Gas‐phase Kinetic and Quantum Chemical Studies of the Reaction of Germylene with Hydrogen Chloride
Authors: Becerra Rosa , Cannady J. Pat , Walsh Robin
Published: February 2023

Time‐resolved studies of germylene, GeH2, generated by laser flash photolysis of 3,4‐dimethyl‐1‐germacyclopent‐3‐ene at 193 nm and monitored by laser absorption, have been carried out to obtain rate constants for its bimolecular reaction with HCl. The reaction was studied in the gas phase, mainly at a total pressure of 10 Torr (in SF6 bath gas) at five temperatures in the range 295–558 K. Experiments at other pressures showed that these rate constants were unaffected by pressure. The second‐order rate constants at 10 Torr (SF6 bath gas) fitted the Arrhenius equation: log(k/cm3 molecule−1 s−1)=(−12.06±0.14)+(2.58±1.03 kJ mol−1)/RTln10 where the uncertainties are single standard deviations. Quantum chemical calculations at G4 level support a mechanism in which an initial weakly bound donor‐acceptor complex is formed. This can then rearrange and decompose to give H2 and HGeCl (chlorogermylene). The enthalpy barrier (36 kJ mol−1) is too high to allow rearrangement of the complex to GeH3Cl (chlorogermane).
Predicting 195Pt NMR Chemical Shifts in Water‐Soluble Inorganic/Organometallic Complexes with a Fast and Simple Protocol Combining Semiempirical Modeling and Machine Learning
Authors: Ondar Evgeniia E. , Polynski Mikhail V. , Ananikov Valentine P.
Published: February 2023

Water‐soluble Pt complexes are the key components in medicinal chemistry and catalysis. The well‐known cisplatin family of anticancer drugs and industrial hydrosylilation catalysts are two leading examples. On the molecular level, the activity mechanisms of such complexes mostly involve changes in the Pt coordination sphere. Using 195Pt NMR spectroscopy for operando monitoring would be a valuable tool for uncovering the activity mechanisms; however, reliable approaches for the rapid correlation of Pt complex structure with 195Pt chemical shifts are very challenging and not available for everyday research practice. While NMR shielding is a response property, molecular 3D structure determines NMR spectra, as widely known, which allows us to build up 3D structure to 195Pt chemical shift correlations. Accordingly, we present a new workflow for the determination of lowest‐energy configurational/conformational isomers based on the GFN2‐xTB semiempirical method and prediction of corresponding chemical shifts with a Machine Learning (ML) model tuned for Pt complexes. The workflow was designed for the prediction of 195Pt chemical shifts of water‐soluble Pt(II) and Pt(IV) anionic, neutral, and cationic complexes with halide, NO2−, (di)amino, and (di)carboxylate ligands with chemical shift values ranging from −6293 to 7090 ppm. The model offered an accuracy (normalized root‐mean‐square deviation/RMSD) of 1.08 %/145.02 ppm on the held‐out test set.
Like‐charge attraction in one‐and two‐dimensional Coulomb systems
Authors: Téllez Gabriel
Published: February 2023

The bare Coulomb interaction between two like‐charges is repulsive. When these charges are immersed in an electrolyte, the thermal fluctuations of the ions turn the bare Coulomb interaction into an effective interaction between the two charges. An interesting question arises: is it possible that the effective interaction becomes attractive for like‐charges? We will show how this like‐charge attraction phenomenon is indeed predicted in some one‐and two‐dimensional models of Coulomb systems. Exact analytical results can be obtained for these Coulomb systems models due to some connections that they have with integrable field theories. We will explain the techniques that allow obtaining exact results for the correlation functions between like‐charge particles and how, under certain circumstances, the natural repulsion interaction shifts to being attractive. Although the technical details differ for 1d or 2d systems, the physical cause of this phenomenon is rooted in a three‐body interaction between the two like‐charges and an ion of the electrolyte with an opposite charge.
Control of a sulfadoxine/trimethoprim combination in the competition horse: Elimination, metabolism and detection following an intravenous administration
Authors: Schenk Ina , Broussou Diane , Roques Beatrice , Lagershausen Henrike , Machnik Marc , Röttgen Helma , Toutain Pierre‐Louis , Thevis Mario
Published: February 2023

The combination of sulfadoxine (SDO) with trimethoprim (TMP) is widely used in veterinarian medicine. The aim of the present study was to compare excretion profiles and detection time windows of SDO and TMP in plasma and urine by means of a validated quantitative method.

Eight horses received a single intravenous (i.v.) dose of 2.7 mg TMP and 13.4 mg SDO per kg bodyweight. Plasma and urine samples were collected up to 15 and 70 days post‐administration, respectively.

While urine samples underwent an enzymatic hydrolysis, plasma samples were proteolysed before further analysis. After solid‐phase extraction, samples were analysed by liquid chromatography/electrospray ionisation tandem mass spectrometry in positive ionisation mode. The applied multiple reaction monitoring (MRM) method allowed the detection of SDO and TMP with a lower limit of detection of 0.03 ng/mL in plasma and 0.2 (SDO) and 0.4 ng/mL (TMP) in urine, respectively. In the present study, detection times for SDO were 15 days in plasma and 49 days in urine, respectively. TMP was detected for up to 7 days in plasma and up to 50 days in urine, respectively. The detection via the TMP metabolite 3‐desmethyl‐trimethoprim was possible for 70 days in urine. Detection times of the other confirmed metabolites N4‐acetylated sulfadoxine, hydroxytrimethoprim, trimethoprim‐1‐oxide and trimethoprim‐3‐oxide were significantly lower.

In order to postulate reasonable screening limits (SLs) to control specific withdrawal times, a Monte Carlo simulation was performed for SDO. The proposed SL of 10 ng/mL SDO in blood and 300 ng/mL urine corresponds to a detection time of 4 days.
Experimentally testing mate preference in an avian system with unidirectional bill color introgression
Authors: McDiarmid Callum S. , Finch Fiona , Peso Marianne , van Rooij Erica , Hooper Daniel M. , Rowe Melissah , Griffith Simon C.
Published: February 2023

Mating behavior can play a key role in speciation by inhibiting or facilitating gene flow between closely related taxa. Hybrid zones facilitate a direct examination of mating behavior and the traits involved in establishing species barriers. The long‐tailed finch (Poephila acuticauda) has two hybridizing subspecies that differ in bill color (red and yellow), and the yellow bill phenotype appears to have introgressed ~350 km eastward following secondary contact. To examine the role of mate choice on bill color introgression, we performed behavioral assays using natural and manipulated bill colors. We found an assortative female mating preference for males of their own subspecies when bill color was not manipulated. However, we did not find this assortative preference in trials based on artificially manipulated bill color. This could suggest that assortative preference is not fixed entirely on bill color and instead may be based on a different trait (e.g., song) or a combination of traits, or alternatively may be due to lower statistical power alongside the bill manipulations being unconvincing to the female choosers. Intriguingly, we find a bias in the inheritance of bill color in captive bred F1 hybrid females. Previous modeling suggests that assortative mate preference and this kind of partial dominance in the underlying genes may together contribute to introgression, making the genetic architecture of bill color in this system a priority for future research.
Functional assessment based on cardiopulmonary exercise testing in mild heart failure: A multicentre study
Authors: Zimerman André , da Silveira Anderson D. , Borges Marina S. , Engster Pedro H.B. , Schaan Thomas U. , de Souza Gabriel C. , de Souza Isabela P.M.A. , Ritt Luiz Eduardo F. , Stein Ricardo , Berwanger Otavio , Vaduganathan Muthiah , Rohde Luis Eduardo
Published: February 2023

Aims

In this multicentre study, we compared cardio‐pulmonary exercise test (CPET) parameters between heart failure (HF) patients classified as New York Heart Association (NYHA) class I and II to assess NYHA performance and prognostic role in mild HF.

Methods and results

We included consecutive HF patients in NYHA class I or II who underwent CPET in three Brazilian centres. We analysed the overlap between kernel density estimations for the per cent‐predicted peak oxygen consumption (VO2), minute ventilation/carbon dioxide production (VE/VCO2) slope, and oxygen uptake efficiency slope (OUES) by NYHA class. Area under the receiver‐operating characteristic curve (AUC) was used to assess the capacity of per cent‐predicted peak VO2 to discriminate between NYHA class I and II. For prognostication, time to all‐cause death was used to produce Kaplan–Meier estimates. Of 688 patients included in this study, 42% were classified as NYHA I and 58% as NYHA II, 55% were men, and mean age was 56 years. Median global per cent‐predicted peak VO2 was 66.8% (IQR 56–80), VE/VCO2 slope was 36.9 (31.6–43.3), and mean OUES was 1.51 (±0.59). Kernel density overlap between NYHA class I and II was 86% for per cent‐predicted peak VO2, 89% for VE/VCO2 slope, and 84% for OUES. Receiving‐operating curve analysis showed a significant, albeit limited performance of per cent‐predicted peak VO2 alone to discriminate between NYHA class I vs. II (AUC 0.55, 95% CI 0.51–0.59, P = 0.005). Model accuracy for probability of being classified as NYHA class I (vs. NYHA class II) across the spectrum of the per cent‐predicted peak VO2 was limited, with an absolute probability increment of 13% when per cent‐predicted peak VO2 increased from 50% to 100%. Overall mortality in NYHA class I and II was not significantly different (P = 0.41), whereas NYHA class III patients displayed a distinctively higher death rate (P < 0.001).

Conclusions

Patients with chronic HF classified as NYHA I overlapped substantially with those classified as NYHA II in objective physiological measures and prognosis. NYHA classification may represent a poor discriminator of cardiopulmonary capacity in patients with mild HF.
Late‐Stage Functionalisation of Pyridine‐Containing Bioactive Molecules: Recent Strategies and Perspectives
Authors: Failla Mattia , Lombardo Giacomo W. , Orlando Paolo , Fiorito Daniele , Bombonato Elena , Ronchi Paolo , Passarella Daniele , Fasano Valerio
Published: February 2023

Late‐Stage Functionalisation (LSF) is an innovative technique that has been successfully applied to the C−H diversification of pharmaceuticals. However, LSF of the pyridine ring in drug‐like molecules is often unselective. As a result, a mixture of structurally related products is obtained, thus making the purification tedious and time‐consuming. This review shines a light on recent strategies addressing the selectivity issue in the LSF of complex natural products or drugs containing the pyridine moiety. Specifically, we have reviewed the efforts reported both in academia and industries with the hope of providing a guide for the LSF of elaborated pyridines.
Catalytic Asymmetric Friedel–Crafts Alkylation of Indole via In Situ Generated Indol‐2‐one
Authors: Fei Yuanai , Hou Jun , Song Huiying , Yang Mei‐li , Lei Pan , Ge Xiayu , Wei Hongbo , Xu Yuanzhen , Xie Weiqing
Published: February 2023

An asymmetric Friedel–Crafts alkylation of indole with in situ generated indol‐2‐one from functionalized 3‐bromooxinidole catalyzed by chiral N,N’‐dioxide/Ni(BF4)2 has been developed. This protocol provides an efficient route to stereoselective construction of a series of 3‐substituted 3’‐indolyloxindoles bearing a quaternary carbon center in excellent yields and enantioselectivities (up to 99 % ee). In addition, the conversion of the resulted 3‐substituted 3’‐indolyloxindole to the key intermediate for the formal synthesis of (+)‐folicanthine was also demonstrated.
5 questions with: Mandy Pennington of Wilkes University
Authors: Talarico Donna
Published: February 2023

We reached out to Mandy Pennington, Director of Digital Strategy at Wilkes University in Wilkes‐Barre, Pennsylvania, to ask her five questions and to learn what strategies have been successful for the central Pennsylvania college.