bluuebunny/crossref_metadata_2025_split huggingface dataset:
NHC‐Organocatalysed Hydroacylation of Unactivated or Weakly Activated C−C Multiple Bonds and Ketones
Authors: Thalakottukara Dolly David , Gandhi Thirumanavelan 
Published: March 2022

AbstractN‐Heterocyclic Carbenes (NHCs) are versatile organocatalysts owing to their umpolung capability – i. e. the catalytic transformation of electrophilic aldehydes into nucleophilic species. Profoundly, aldehyde umpolungs were exploited in Benzoin and Stetter reactions, whereas hydroacylation of unactivated carbon‐carbon multiple bonds (alkenes and alkynes) are challenging and highly desired. Normally, catalytic hydroacylation of alkenes was achieved by transition metal catalysts based on rhodium, cobalt, nickel, ruthenium, and iridium. However, the metal‐catalyzed strategy is accompanied by undesired side reactions, such as decarbonylation of aldehydes, and thus demands installation of directing group in the aldehydes. In contrast, NHCs overcome these downsides and utilize the umpolung strategy beyond the Benzoin and Stetter reactions to implement catalytic hydroacylation of unpolarised and unactivated carbon‐carbon multiple bonds (alkenes and alkynes) under mild reaction conditions with step‐ and atom‐economy. In addition, this unconventional transformation is extended to catalytic asymmetric catalysis. This highlight covers the progress and practicality of NHC‐catalyzed hydroacylation of alkenes, alkynes, arynes, and ketones to access biologically relevant organics. Both inter‐and intramolecular hydroacylation reactions in combination with Stetter were presented and key mechanistic pathways were discussed.
Photothermal Nanoconfinement Reactor: Boosting Chemical Reactivity with Locally High Temperature in a Confined Space
Authors: Zhang Han‐Chao , Kang Zhan‐Xiao , Han Jiang‐Jin , Wang Peng , Fan Jin‐Tu , Sheng Guo‐Ping 
Published: March 2022

AbstractA photothermal nanoconfinement reactor (PNCR) system is proposed and demonstrated by using hollow carbon nanospheres (HCNs) to enhance the performance of the chemical reaction. Under light irradiation, the local temperature of the HCN inner void space was much higher than the bulk solution temperature because the confined space concentrates heat and inhibits heat loss. Using the temperature‐sensitive model reaction, peroxydisulfate (PDS) activation to oxidize micropollutant, it is shown that the degradation rate of sulfamethoxazole in the PNCR system is 7.1 times of that without nanoconfinement. It is further discovered that the high‐quality local heat inside the nanoconfined space shifted the model reaction from an otherwise non‐radical pathway to a radical‐based pathway. This work provides an interesting strategy to produce a locally high temperature, which has a wide range of applications to energy and environmental fields.
Hierarchical Self‐Assembly of Adhesive and Conductive Gels with Anion‐Coordinated Triple Helicate Junctions
Authors: Gao Yiwei , Zhao Jie , Huang Zehuan , Ronson Tanya K. , Zhao Fen , Wang Yue , Li Boyang , Feng Chenlu , Yu You , Cheng Yongliang , Yang Dong , Yang Xiao‐Juan , Wu Biao 
Published: March 2022

AbstractThe fabrication of anion‐coordinated assemblies into functional soft materials remains a major challenge. To this end, four C2‐symmetric anion‐binding ligands equipped with ortho‐phenylene‐bridged bis(urea) and amine or amide ends were designed, which generated A2L3 triple helical architectures upon self‐assembly with phosphate ions. Hierarchical intermolecular hydrogen bonds among the terminal amine/amide groups and urea moieties resulted in the formation of functional gels. The obtained gels were further applied for conductive adhesion between different surfaces, displaying excellent flexibility and selective wettability. The viscoelastic gels constructed from anion‐coordinated assemblies described in this work represent the first example of a new class of anion‐coordination‐driven smart materials.
Korrelative elektrochemische Mikroskopie zur Aufklärung der lokalen ionischen und elektronischen Eigenschaften der Festkörper‐Elektrolyt Zwischenphase in Li‐Ionen‐Batterien
Authors: Santos Carla S. , Botz Alexander , Bandarenka Aliaksandr S. , Ventosa Edgar , Schuhmann Wolfgang 
Published: March 2022

AbstractDie Festkörper‐Elektrolyt‐Zwischenphase (SEI) spielt eine Schlüsselrolle für die Stabilität von Lithium‐Ionen‐Batterien (LIB), da die SEI den kontinuierlichen Abbau des Elektrolyten an der Anode verhindert. Die SEI fungiert als isolierende Schicht für den Elektronentransfer und ermöglicht dennoch den Ionenfluss durch die Schicht. Wir kombinieren zum ersten Mal die Rückkopplungs‐ und Multifrequenz‐Wechselstrommodi der elektrochemischen Rastermikroskopie (SECM), um die lokalen elektronischen und ionischen Eigenschaften der SEI quantitativ zu bewerten, indem wir die SEI‐Bildungsbedingungen und die verwendeten Elektrolyte der Li‐Ionen‐Batterien variieren. Korrelationen zwischen den elektronischen und ionischen Eigenschaften der resultierenden SEI auf einer Modell‐Cu‐Elektrode zeigen die Machbarkeit der vorgeschlagenen Strategie, um die beiden wesentlichen Eigenschaften einer SEI zu quantifizieren: ionische und elektronische Leitfähigkeit in Abhängigkeit von den Bildungsbedingungen; Ergebnisse, die voraussichtlich einen signifikanten Einfluss auf den Bereich der LIBs haben werden.
Metal→Carbon Dative Bonding
Authors: Litle Elishua D. , Gabbaï François P. 
Published: March 2022

AbstractAs part of our interest in unusual bonding situations, we are now targeting complexes featuring metal→carbon dative bonds. Here, we report on the formation of such linkages in a series of Group 10 complexes featuring a triarylphosphine ligand functionalized at the γ position by a carbenium ion. Through combined synthetic, spectroscopic, and computational studies, we show that the M→Ccarbenium interaction present in these complexes scales with the basicity of the donor, confirming its dative nature.
Angiopep‐2 and cyclic RGD dual‐targeting ligand modified micelles across the blood–brain barrier for improved anti‐tumor activity
Authors: Lei Yujie , Chen Shihong , Zeng Xuan , Meng Yan , Chang Cong , Zheng Guohua 
Published: March 2022

AbstractIn this paper, three polymers of Angiopep‐2 conjugated polyethylene glycol (PEG)‐β‐cyclodextrin (Ang‐2‐PEG‐βCD), cyclic RGD (cRGD)‐PEG‐βCD, Ad‐PCL‐FITC and corresponding double‐targeted polymer micelles (D‐T micelles) were successfully prepared by host–guest self‐assembly. Transmission electron microscope images showed that uniformly dispersed spherical supermolecular micelles could be formed. The colloidal stability of D‐T micelles in 5% glucose and 10% FBS solution were good within 24 h, which was fine in distilled water at room temperature within 2 weeks. The results of fluorescence microscope and flow cytometry demonstrating the prepared double‐targeted micells showed high intracellular delivery efficiency in both brain microvascular endothelial cells (bEnd.3 cell) and glioma cells (C6 cell). As expected, based on the specific recognition between the peptides and the receptors, the D‐T micelles exhibited better anti‐tumor efficacy than free chemotherapy drug and non‐targeted micelles both in vitro and in vivo, indicating the great potential of D‐T micelles developed here as promising vehicle for glioma targeted drug delivery.
Green cross‐linked coir cellulose nanocrystals/poly (vinyl alcohol) composite films with enhanced water resistance, mechanical properties, and thermal stability
Authors: Rao Xin , Ou Zhiqiang , Zhou Qi , Fu Lingying , Gong Yue , Wen Qin , Du Xueyu , Liang Chen 
Published: March 2022

AbstractPoly(vinyl alcohol) (PVA) based materials have received enormous attention ascribed to the merits of good mechanical properties, biodegradability, and environmental friendliness, but its widespread applications are severely hindered by poor water resistance. In the current study, self‐made coir cellulose nanocrystal (CCNC) was applied as a reinforcing filler together with a cost‐effective and green cross‐linker (oxalic acid, OA) for preparation of CCNC/OA/PVA composite film via solution casting. After the thermal treatment of 120°C for 2 h, the ultimate product exhibited remarkable improvements in tensile strength (132.4 MPa), Young's modulus (4427.1 MPa), water resistance (degree of swelling: 33.6%; contact angle: 84.7°; solubility: 0.9%), and thermal stability relative to the cleavage of the polymer chains (depolymerization). A reinforced synergetic effect of physical interaction (hydrogen bond) and hydrophobic ester linkages has been suggested according to the comprehensive analyses of functional groups, crystal structure, thermal behavior and stability, and fracture surface morphology.
Rational engineering in Escherichia coli for high‐titer production of baicalein based on genome‐scale target identification
Authors: Ji Dongni , Li Jianhua , Ren Yuhong , Wang Yong 
Published: March 2022

AbstractBaicalein is a bioactive flavonoid isolated from the traditional Chinese medicinal plant, Scutellaria baicalensis Georgi. Microbial synthesis of flavonoids has been intensively developed owing to the eco‐friendly nature of the process. However, the titer of the flavonoids obtained is still at a low level, and effective methods to enhance these titers are lacking. In this study, the synthetic performance of baicalein‐producing engineered Escherichia coli was rationally evaluated to enhance the expression of key enzymes. Transcriptional analyses of baicalein‐overproducing strain and a control strain enabled the identification of 13 beneficial genes, including eight genes that are seemingly irrelevant to baicalein metabolism. With the combination of the enzyme assembly and modularization strategy, the engineered DN‐8 strain produced 367.8 mg/L baicalein in fed‐batch fermentation, the maximum titer reported to date.
Analysis of clinical characteristics and prognostic factors in 110 patients with nitrous oxide abuse
Authors: Yu Miao , Qiao Yue , Li Weishuai , Fang Xiuying , Gao Han , Zheng Dongming , Ma Ying 
Published: March 2022

AbstractPurposeTo review the clinical symptoms, auxiliary examination findings, and outcomes of patients with nitrous oxide (N2O) abuse, and analyze the factors that affect outcomes.MethodsPatients with N2O abuse treated in the Department of Neurology between January 2018 and December 2020 were included. The clinical data of these patients were collected, and follow‐up was conducted to determine the outcomes.ResultsThe average age of the 110 patients with N2O abuse was 21.4 ± 4.2 years (range: 14–33 years). Clinical presentation primarily included neurological symptoms, such as limb numbness and/or weakness (97%), psychiatric symptoms, changes in appetite, and skin hyperpigmentation. Laboratory test results were characterized by vitamin B12deficiency (60%, 34 out of 57 cases) and high homocysteine level (69%, 31 out of 45 cases). Electromyography indicated mixed axonal and demyelination injury (92%, 80 out of 87 cases). Motor and sensory nerves were simultaneously involved, and injury primarily involved the lower limbs. One hundred and seven (97%) patients were clinically diagnosed with peripheral neuropathy, of whom 26 (24%) exhibited spinal abnormalities on magnetic resonance imaging, supporting a diagnosis of subacute combined degeneration. Treatment included N2O withdrawal and vitamin B12supplementation. Reexamination of six patients indicated that treatment was effective. Follow‐up was completed for 51 patients. Thirty‐four patients (67%) recovered completely, 17 patients (33%) had residual limb numbness, and only one patient experienced relapse. Sex was an independent prognostic factor; the outcomes of female patients were better than that of male patients.ConclusionThe recreational use of N2O has largely expanded among youth in recent decades, which has become a growing public health concern in China. It highlights the importance of the recognition of various clinical symptoms, particularly limb numbness and/or weakness related to the cases of N2O abuse. The therapeutic administration of vitamin B12supplementation and N2O withdrawal can make the overall prognosis good, especially for female patients.
An all Prussian blue analog‐based aprotic sodium‐ion battery
Authors: Xu Li , Li Hui , Du Ting , Xue Qing , Gao Yuting , Yu Zhuangzhuang , Bai Huitao 
Published: March 2022

AbstractSodium‐ion batteries have been regarded as ideal alternatives to lithium‐ion batteries in large‐scale electrochemical energy storage systems because of their low cost and abundant resources. However, the lack of high‐performance electrode materials with high energy density hinders the development of sodium‐ion batteries. Prussian blue analogs (PBAs) are especially regarded as superior cathodes for sodium‐ion batteries due to their high capacity and good electrochemical stability. The species and chemical environment of transition metal ions in PBAs greatly affect the electrochemical properties. In this study, we report a sodium cobalt hexacyanoferrate (NaxCo[Fe(CN)6]) and potassium iron hexacyanocobaltate (KxFe[Co(CN)6]) nanoparticles through the coprecipitation method via changing the coordination structures of Co and Fe. With similar morphologies of well‐defined nanocubes and different M1–CN–Mʹ2, the initial discharge capacities of NaxCo[Fe(CN)6] cathode and KxFe[Co(CN)6] anode reach 104.1 and 354.8 mAh g−1, respectively. The sodium‐ion full cell assembled using NaxCo[Fe(CN)6] cathode and KxFe[Co(CN)6] anode achieves a discharge capacity of 141.6 mAh g−1. The outstanding performances of the NaxCo[Fe(CN)6] and KxFe[Co(CN)6] are attributed to their stable structures, and the facile synthesis of NaxCo[Fe(CN)6] and KxFe[Co(CN)6] makes them accessible for large‐scale applications.
Retrospective analysis of adjuvant treatment for localized, operable uterine leiomyosarcoma
Authors: Chantharasamee Jomjit , Wong Karlton , Potivongsajarn Pasathorn , Qorbani Amir , Motamed Neda , Brackert Sandra , Cohen Joshua , Chmielowski Bartosz , Kalbasi Anusha , Rao Jianyu , Nelson Scott , Singh Arun 
Published: March 2022

AbstractObjectiveCurrently, there is no standard adjuvant treatment protocol for localized uterine leiomyosarcoma (uLMS) as clinical trials to address this question have been retrospective, underpowered, or undermined by slow accrual rates. The aim of this study is to determine the benefit of adjuvant chemotherapy for uLMS.MethodsWe reviewed the medical records of localized uLMS patients who had underwent adjuvant therapy after upfront surgery between 2000 and 2020. The cases were blinded for review. We evaluated the influence of various clinical characteristics and different types of adjuvant therapies on specific outcomes.ResultsSixty‐eight patients (median age: 50 years) were included for analysis. Forty of 68 (58.8%) patients received adjuvant chemotherapy +/− radiation therapy and 25 patients (38.6%) did not receive any adjuvant therapy. At a median follow‐up time of 43.3 months, 45 patients (66.1%) had relapsed disease. The median disease‐free survival (mDFS) for all patients was 23.1 months. Patients who received any adjuvant treatment (chemotherapy and/or radiation) trended toward a longer mDFS compared with those who did not receive any adjuvant therapy (29.7 vs. 14.1 months, p = 0.26). Patients who received adjuvant chemotherapy alone had a longer, but nonstatistically significant mDFS compared with those who did not receive any adjuvant treatment (22.2 vs. 14.1 months, p = 0.18). Additionally, univariate analysis found that tumor size large than 10 cm, and a mitotic rate >10/10hpf were independent prognostic factors for worse DFS.ConclusionsThough DFS was more favorable among those who received adjuvant therapy, it was not statistically significant, and thus based on this data adjuvant therapy for resected uLMS is still in question.
Effect of systemic therapies or best supportive care after disease progression to both nivolumab and cabozantinib in metastatic renal cell carcinoma: The Meet‐Uro 19BEYOND study
Authors: Roviello Giandomenico , Gambale Elisabetta , Giorgione Roberta , Santini Daniele , Stellato Marco , Fornarini Giuseppe , Rebuzzi Sara Elena , Basso Umberto , Bimbatti Davide , Doni Laura , Nesi Gabriella , Bersanelli Melissa , Buti Sebastiano , De Giorgi Ugo , Galli Luca , Sbrana Andrea , Conca Raffaele , Carella Claudia , Naglieri Emanuele , Pignata Sandro , Procopio Giuseppe , Antonuzzo Lorenzo 
Published: March 2022

AbstractBackgroundNivolumab and cabozantinib are currently approved agents in metastatic renal cell carcinoma (mRCC) but there are no data available for patients progressing to both treatments. The aim of this study was to compare active therapeutic options and best supportive care (BSC) after progression to nivolumab and cabozantinib in mRCC.MethodsIn this retrospective study, we selected 50 patients from eight Italian centers. The primary endpoint of the study was the overall survival (OS) of patients on active treatment versus BSC. Secondary endpoints were the progression‐free survival (PFS) and objective response rate (ORR). The efficacy of active therapy was also investigated.ResultsAfter progression to both nivolumab and cabozantinib, 57.1% of patients were given active treatment (mainly everolimus and sorafenib) while 42.9% received BSC. The median OS was 13 months (95% CI: 4‐NR) in actively treated patients and 3 months (95% CI: 2–4) in BSC patients (p = 0.001). Patients treated with sorafenib had better disease control than those treated with everolimus (stable disease: 71.4% vs. 16.7%, progression disease: 14.3% vs. 58.3%; p = 0.03), with no significant differences in PFS (5 and 3 months, 95% CI: 1–6 vs. 2–5; p = 0.6) and OS (12 and 4 months, 95% CI: 3‐NR vs. 2‐NR; p = 0.2).ConclusionAfter treatment with both nivolumab and cabozantinib, the choice of a safe active systemic therapy offered better outcomes than BSC.
Synthesis of Evodileptin B, a Natural Anthranilate Derivative Isolated from Evodia lepta, and Evaluation of Its Therapeutic Potential against Parkinson's Disease
Authors: Kim Soobin , Yang Wooin , Cha Dong Seok , Han Young Taek 
Published: March 2022

AbstractEvodileptin B (1) is a natural anthranilate derivative isolated from the ethanol extract of the aerial parts of Evodia lepta (Spreng.) Merr., a traditional medicinal plant of the family Rutaceae. We readily synthesized 1 via the amidation of phloretic with methyl anthranilate and evaluate its neuroprotective activity using a C. elegans Parkinson's disease (PD) model. The results showed that evodilpetin B ameliorated MPP+‐induced dopaminergic (DA) neurodegeneration in a dose‐dependent manner. Evodileptin B treatment also significantly improved the DA neurotransmission‐related behavioral defects such as reduced locomotory and food‐sensing ability of worms under MPP+ exposure conditions, suggesting its potential application for the functional restoration of DA neurons. In addition, we found that 1 has an ability to regulate aggregation of α‐synuclein by increasing proteasome activity in the human α‐synuclein‐expressing mutant worms. These results demonstrate that evodileptin B has strong neuroprotective properties and may be useful in the treatment of PD.
Hypopurolides A – G, Labdane Diterpenoids from Hypoestes purpurea and Their Nitric Oxide Inhibitory Activity
Authors: Ding Lin‐Fen , Cheng Bin , Lei Tie , Liu Zhen‐Xiang , Zhao Xue‐Yu , Song Liu‐Dong , Zhao Qin‐Shi 
Published: March 2022

AbstractSeven new labdane diterpenoids, hypopurolides A–G (1–7) were discovered from the aerial part of Hypoestes purpurea, along with one known analog, hypopurin D (8). The structures of 1–7 were characterized based on 1H‐, 13C‐, and 2D‐NMR, and HR‐ESI‐MS spectra. The absolute configurations of 1–7 were defined by single‐crystal X‐ray diffraction and electronic circular dichroism (ECD) data. Compounds 1–8 were tested for their nitric oxide (NO) inhibitory and cytotoxic effects. Compound 6 displayed moderate inhibitory effect toward LPS‐induced NO release in RAW 264.7 cells with an IC50 value of 41.50 μM.
Outcomes and feasibility of redo‐TAVR after Sapien 3 Ultra TAVR in extremely‐undersized versus nominally‐sized annuli
Authors: Tang Gilbert H. L. , Hooda Amit , Zaid Syed , Chuang Ming‐Yu , Khera Sahil , Krishnamoorthy Parasuram , Lerakis Stamatios , Anastasius Malcolm , Ahmad Hasan A. , Goldberg Joshua B. , Akodad Mariama , Wood David A. , Leipsic Jonathon A. , Blanke Philipp , Dangas George D. , Sharma Samin K. , Kini Annapoorna S. , Webb John G. , Sathananthan Janarthanan 
Published: March 2022

AbstractObjectivesTo compare outcomes in Sapien 3 Ultra (S3U) transcatheter aortic valve replacement (TAVR) with extreme annular undersizing (EAU) versus nominal annular sizing (NAS).BackgroundThe Edwards S3U valve has reduced paravalvular leak (PVL) in TAVR but outcomes remain unknown in extremely undersized anatomy. Implanting a smaller S3U valve may facilitate future redo‐TAVR but risk compromising hemodynamics.MethodsFrom December 2019 to July 2021, 366 patients with native aortic stenosis underwent S3U TAVR. Patients with EAU (annular areas >430 mm2 for 23 mm or >546 mm2 for 26 mm) were compared to NAS (338–430 mm2 for 23 mm or 430–546 mm2 for 26 mm). In‐hospital and 30‐day outcomes, and redo‐TAVR feasibility were determined.ResultsThere were 79 (21.6%) EAU patients, with more bicuspid (p = 0.0014) and ≥moderate annular/left ventricular outflow tract calcification (p < 0.001). The EAU group had less annular oversizing than NAS group (23 mm: −8.2 ± 2.6% vs. 4.0 ± 7.0%, p < 0.001; 26 mm: −8.9 ± 2.2% vs. 6.7 ± 6.9%, p < 0.001), more balloon overfilling (71.3% vs. 11.6%, p < 0.001), and postdilatation (15.0% vs. 5.8%, p = 0.016). No differences were found in in‐hospital or 30‐day mortality and stroke (p > 0.05). Mild PVL (13.4% EAU vs. 11.5% NAS, p = 0.56) and mean gradients (23 mm: 13.0 ± 4.5 vs. 14.1 ± 5.4 mmHg, p = 0.40; 26 mm: 11.4 ± 4.1 vs. 11.5 ± 3.9 mmHg, p = 1.0) were similar at 30 days. Had the EAU group undergone NAS with the larger Sapien 3/S3U, by computed tomography analysis simulating 80:20 or 90:10 target implant depth, 33.3%–60.9% (vs. 4.3%–23.2%) would not be feasible for redo‐TAVR due to high risk of coronary obstruction.ConclusionsIn this first report of EAU with S3U TAVR, similar excellent short‐term outcomes can be achieved compared to NAS, and may preserve future redo‐TAVR option.