bluuebunny/crossref_metadata_2025_split huggingface dataset:
Heterogeneous Copper‐Catalyzed Cross‐Coupling for Sustainable Synthesis of Chiral Allenes: Application to the Synthesis of Allenic Natural Products
Authors: Wu Haibo , Zheng Zhiyao , Zhang Kaiheng , Kajanus Johan , Johansson Magnus J. , Córdova Armando , Bäckvall Jan‐E. 
Published: October 2023

AbstractClassical Crabbé type SN2' substitutions of propargylic substrates has served as one of the standard methods for the synthesis of allenes. However, the stereospecific version of this transformation often requires either stoichiometric amounts of organocopper reagents or special functional groups on the substrates, and the chirality transfer efficiency is also capricious. Herein, we report a sustainable methodology for the synthesis of diverse 1,3‐di and tri‐substituted allenes by using a simple and cheap cellulose supported heterogeneous nanocopper catalyst (MCC‐Amp‐Cu(I/II)). This approach represents the first example of heterogeneous catalysis for the synthesis of chiral allenes. High yields and excellent enantiospecificity (up to 97 % yield, 99 % ee) were achieved for a wide range of di‐ and tri‐substituted allenes bearing various functional groups. It is worth noting that the applied heterogeneous catalyst could be recycled at least 5 times without any reduced reactivity. To demonstrate the synthetic utility of the developed protocol, we have applied it to the total synthesis of several chiral allenic natural products.
Recent Developments with Organogermanes: their Preparation and Application in Synthesis and Catalysis
Authors: Rogova Tatiana , Ahrweiler Eric , Schoetz Markus D. , Schoenebeck Franziska 
Published: October 2023

AbstractWithin the sphere of traditional Pd0/PdII cross coupling reactions, organogermanes have been historically outperformed both in terms of scope and reactivity by more conventional transmetalating reagents. Subsequently, this class of compounds has been largely underutilized as a coupling partner in bond‐forming strategies. Most recent studies, however, have shown that alternative modes of activation of these notoriously robust building blocks transform organogermanes into the most reactive site of the molecule—capable of outcompeting other functional groups (such as boronic acids, esters and silanes) for both C−C and C–heteroatom bond formation. As a result, over the past few years, the literature has increasingly featured methodologies that explore the potential of organogermanes as chemoselective and orthogonal coupling partners. Herein we highlight some of these recent advances in the field of organogermane chemistry both with respect to their synthesis and applications in synthetic and catalytic transformations.
A Single‐Enantiomer Emitter Enabled Superstructural Helix Inversion for Upconverting and Downshifting Luminescence with Bidirectional Circular Polarization
Authors: Ren Chao , Sun Wenjing , Zhao Tonghan , Li Chengxi , Jiang Chengyu , Duan Pengfei 
Published: October 2023

AbstractThe helical twisting tendency of liquid crystals (LCs) is generally governed by the inherent configuration of the chiral emitter. Here, we introduce the multistage inversion of supramolecular chirality as well as circularly polarized luminescence (CPL) by manipulating the ratio of single enantiomeric emitters (R‐PCP) to LC monomers (5CB). Increasing the content of R‐PCP from 1 wt % to 3 wt % inverted the helix of LCs from left‐handed to right‐handed, accompanying a CPL sign changed from positive to negative. The biaxiality of chiral emitters, as well as the steric effect of chiral‐chiral and chiral‐achiral interaction, were identified as the reasons for helical sense inversion. Due to the strong helical twisting power, 4 wt % R‐PCP drove the photonic band gap (PBG) of chiral LCs to match up with their emission range, leading to an inversion of the CPL again with a high dissymmetry factor (≈1.2). Directly adjusting the PBG using chiral emitters is seldom achieved in cholesteric LCs. On this basis, an achiral sensitizer PtTPBP was assembled into the helical superstructure. The generation of triplet‐triplet annihilation‐induced upconverted CPL from R‐PCP and the downshifting CPL from PtTPBP with opposite rotation was achieved in a single chiral LC system by tuning the position of the PBG.
Doctor Versus Artificial Intelligence: Patient and Physician Evaluation of Large Language Model Responses to Rheumatology Patient Questions in a Cross‐Sectional Study
Authors: Ye Carrie , Zweck Elric , Ma Zechen , Smith Justin , Katz Steven 
Published: October 2023

ObjectiveThe objective of the current study was to assess the quality of large language model (LLM) chatbot versus physician‐generated responses to patient‐generated rheumatology questions.MethodsWe conducted a single‐center cross‐sectional survey of rheumatology patients (n = 17) in Edmonton, Alberta, Canada. Patients evaluated LLM chatbot versus physician‐generated responses for comprehensiveness and readability, with four rheumatologists also evaluating accuracy by using a Likert scale from 1 to 10 (1 being poor, 10 being excellent).ResultsPatients rated no significant difference between artificial intelligence (AI) and physician‐generated responses in comprehensiveness (mean 7.12 ± SD 0.99 vs 7.52 ± 1.16; P = 0.1962) or readability (7.90 ± 0.90 vs 7.80 ± 0.75; P = 0.5905). Rheumatologists rated AI responses significantly poorer than physician responses on comprehensiveness (AI 5.52 ± 2.13 vs physician 8.76 ± 1.07; P < 0.0001), readability (AI 7.85 ± 0.92 vs physician 8.75 ± 0.57; P = 0.0003), and accuracy (AI 6.48 ± 2.07 vs physician 9.08 ± 0.64; P < 0.0001). The proportion of preference to AI‐ versus physician‐generated responses by patients and physicians was 0.45 ± 0.18 and 0.15 ± 0.08, respectively (P = 0.0106). After learning that one answer for each question was AI generated, patients were able to correctly identify AI‐generated answers at a lower proportion compared to physicians (0.49 ± 0.26 vs 0.97 ± 0.04; P = 0.0183). The average word count of AI answers was 69.10 ± 25.35 words, as compared to 98.83 ± 34.58 words for physician‐generated responses (P = 0.0008).ConclusionRheumatology patients rated AI‐generated responses to patient questions similarly to physician‐generated responses in terms of comprehensiveness, readability, and overall preference. However, rheumatologists rated AI responses significantly poorer than physician‐generated responses, suggesting that LLM chatbot responses are inferior to physician responses, a difference that patients may not be aware of.image
Do we have to rethink inclusive pedagogies for secondary schools? A critical systematic review of the international literature
Authors: Koutsouris George , Bremner Nicholas , Stentiford Lauren 
Published: October 2023

AbstractThis article builds on the findings of a critical systematic review that aimed to explore understandings and applications of inclusive pedagogies in the secondary school. Inclusive pedagogies are often conceptualised as both a set of strategies that aim to ensure access to learning for all students, and as value principles that reflect particular views on inclusion; this is why they tend to be approached in diverse ways. We were particularly interested in secondary school as the focus on particular curricular areas and subjects, additional pressures for teachers and students derived from assessment and exams, and fewer opportunities for collaboration between teachers as a result of the compartmentalisation of the curriculum can make the implementation of inclusive pedagogies more challenging than at primary level. Six databases were searched for literature published exploring inclusive pedagogies in the context of secondary school. We found that inclusive pedagogies were often filtered through the lenses of particular subjects and were associated with other approaches with similar philosophies, such as differentiation and student‐centred learning; that student perceptions of inclusive pedagogies are still little explored; and that tensions associated with inclusion were only acknowledged to some extent. Based on the findings, we argue for a refined way of understanding inclusive pedagogies in the secondary school context, one that acknowledges the unique characteristics, challenges and tensions at this school level. The review findings also affirm the ‘messiness’ of the inclusion literature and raise questions as to the relevance and usefulness of systematic reviews in exploring this fragmented topic.
Over 104‐fold amplified upconversion luminescence of lanthanide nanocrystals through optical oscillator‐like system
Authors: Zhu Xinyan , Yang Mingzhu , Zhang Hongxin 
Published: October 2023

AbstractRecently, lanthanide (Ln) luminescent nanocrystals have attracted increasing attention in various fields such as biomedical imaging, lasers, and anticounterfeiting. However, due to the forbidden 4f–4f transition of lanthanide ions, the absorption cross‐section and luminescence brightness of lanthanide nanocrystals are limited. To address the challenge, we constructed an optical oscillator‐like system to repeatedly simulate lanthanide nanocrystals to enhance the absorption efficiency of lanthanide ions on excitation photons. In this optical system, the upconversion luminescence (UCL) of Tm3+ emission of ~450 nm excited by a 980 nm laser can be amplified by a factor beyond 104. The corresponding downshifting luminescence of Tm3+ at 1460 nm was enhanced by three orders of magnitude. We also demonstrated that the significant luminescence enhancement in the designed optical oscillator‐like system was general for various lanthanide nanocrystals including NaYF4:Yb3+/Ln3+, NaErF4@NaYF4 and NaYF4:Yb3+/Ln3+@NaYF4:Yb3+@NaYF4 (Ln = Er, Tm, Ho) regardless of the wavelengths of excitation sources (808 and 980 nm). The mechanism study revealed that both elevated laser power in the optical system and multiple excitations on lanthanide nanocrystals were the main reason for the luminescence amplification. Our findings may benefit the future development of low‐threshold upconversion and downshifting luminescence of lanthanide nanocrystals and expand their applications.
Detection and elimination of trace d‐lactic acid in lignocellulose biorefining chain: Generation, flow, and impact on chiral lactide synthesis
Authors: Guo Xiaomeng , Li Zhibin , He Niling , Zhang Bin , Liu Xiucai , Bao Jie 
Published: October 2023

AbstractHigh chiral purity of lactic acid is a crucial indicator for the synthesis of chiral lactide as the primary intermediate chemical for ring‐open polymerization of high molecular weight polylactic acid (PLA). Lignocellulose biomass is the most promising carbohydrate feedstock for commercial production of PLA, but the presence of trace d‐lactic acid in the biorefinery chain adversely affects the synthesis and quality of chiral lactide. This study analyzed the fingerprint of trace
d‐lactic acid in the biorefinery chain and found that the major source of
d‐lactic acid comes from lignocellulose feedstock. The naturally occurring lactic acid bacteria and water‐soluble carbohydrates in lignocellulose feedstock provide the necessary conditions for
d‐lactic acid generation. Three strategies were proposed to eliminate the generation pathway of
d‐lactic acid, including reduction of moisture content, conversion of water‐soluble carbohydrates to furan aldehydes in pretreatment, and conversion to
l‐lactic acid by inoculating engineered
l‐lactic acid bacteria. The natural reduction of lactic acid content in lignocellulose feedstock during storage was observed due to the lactate oxidase‐catalyzed oxidation of
l‐ and
d‐lactic acids. This study provided an important support for the production of cellulosic
l‐lactic acid with high chiral purity.
The effect of body mass index on quality of life in modified single stoma cutaneous ureterostomy or ileal conduit after radical cystectomy
Authors: Zhang Wan‐Jin , Huang Xu‐Yun , Lin Bin , Zheng Wen‐Cai , Ke Zhi‐Bin , Lin Xiao‐Dan , Chen Jia‐Yin , Cai Hai , Lin Yun‐Zhi , Chen Ye‐Hui , Zheng Qing‐Shui , Wei Yong , Xue Xue‐Yi , Li Xiao‐Dong , Xu Ning 
Published: October 2023

AbstractObjectiveTo explore the influence of postoperative body mass index (BMI) change on postoperative quality of life (QOL) in patients undergoing radical cystectomy (RC) plus modified single stoma cutaneous ureterostomy (MSSCU) or ileal conduit (IC).MethodsPatients were divided into two groups according to different BMI change patterns: patients experiencing an elevated postoperative BMI level, along with a clinically significant increase in their BMI (an increase of more than 10%) were categorized as Group 1, while patients experiencing a decrease postoperative BMI level, along with a clinically significant reduction in their BMI (a decrease of more than 5%) were categorized as Group 2. Spearman correlation analysis was used to examine the correlations between quality‐of‐life scores and postoperative clinical parameters.ResultsSpearman correlation analysis showed that postoperative BMI, late complications and catheter‐free state were significantly associated with postoperative global QoL and symptom scale in MSSCU and postoperative global QoL and physical scale in IC patients. Additionally, postoperative BMI, catheter‐free state and the use of adjuvant therapy were associated with bad performance in many scales of QoL like body image, future perspective, social scale, future perspective (MSSCU), and abdominal bloating (IC) (Table 2, p<0.05). Patients in Group 2 with significant weight loss had a better Global QoL, a lower rate of stomal stricture and a higher catheter‐free state compared with those in Group 1 in both IC and MSSCU patients. MSSCU patients in Group 2 could achieve a comparable Global QoL as to IC patients in Group 1.ConclusionControlling the substantial increase in body weight after surgery contributes to improving QoL, reducing the occurrence of stomal stricture, and ensuring a postoperative catheter‐free state in BCa patients undergoing MSSCU.
Comparative analysis of clinicopathologic characteristics and prognosis between nasal and nonnasal extranodal NK/T‐cell lymphoma
Authors: Shen Ziyuan , Chen Xicheng , Sun Cai , Lu Tianyi , Shi Yuye , Zhang Hao , Ye Jingjing , Wang Ling , Zhu Taigang , Miao Yuqing , Zhang Xudong , Wang Liang , Cai Guoqi , Sang Wei 
Published: October 2023

AbstractBackgroundThe clinicopathologic characteristics and prognosis of nasal and nonnasal extranodal natural killer T‐cell lymphoma (ENKTL) are considered to be different. However, the underlying features responsible for these differences are not well clarified especially in the era of asparaginase therapy.MethodsIn total, 1007 newly diagnosed ENKTL patients from 11 medical centers were included in this study. Clinicopathologic characteristics and survival data were collected. The chi‐squared test and Kruskal–Wallis test were utilized for the comparison of different groups. Univariable and multivariable Cox proportional hazards models were used to screen prognostic factors.ResultsOverall, 869 (86.3%) patients were nasal forms. Compared to patients with nasal ENKTL, nonnasal patients were at more advanced stages and had poor performance status, bone marrow involvement, elevated serum lactate dehydrogenase (LDH), and CD56‐negative status (p < 0.05). The 5‐year overall survival (OS) for nasal and nonnasal patients were 65.6% and 45.0%, respectively. The OS of nasal forms patients were superior to nonnasal patients, especially in Eastern Cooperative Oncology Group performance status (ECOG PS) (≥2), advanced stage, KPI (HIR/HR), IPI (HIR/HR), PINK (HR), and high EBV DNA load groups. In patients treated with pegaspargase/L‐asparaginase‐based regimens, the OS of nasal patients was better than that of nonnasal patients. After adjusting the covariates of age, stage, ECOG PS score, LDH, B symptoms, and BM involvement, results showed that the nonnasal site was associated with poor survival of ENKTL.ConclusionsThe clinicopathologic characteristics and prognosis of nasal and nonnasal ENKTL patients are different. Nasal forms patients had superior OS than nonnasal patients, especially in the era of asparaginase.
Easy to Use DFT Approach for Computational pKa Determination of Carboxylic Acids
Authors: Pezzola Silvia , Venanzi Mariano , Galloni Pierluca , Conte Valeria , Sabuzi Federica 
Published: October 2023

AbstractIn pKa computational determination, the challenge in exploring and fostering new methodologies and approaches goes in parallel with the amelioration of computational performances. In this paper a “ready to use methodology” has been compared to other strategies, such as the re‐shaping in solvation cavity (Bondi radius re‐shaping), wanting to assess its reliability in predicting the pKa of a broad list of carboxylic acids. Thus, the functionals B3LYP and CAM‐B3LYP have been selected, using SMD as continuum solvation model. Exploiting our previous results, two water molecules were made explicit on the reaction centre. Data show that our model (CAM‐B3LYP/2H2O) is capable to accurately predict pKa, leading to mean absolute error (MAE) values lower than 0.5. Noteworthy, good results were achieved in computing the pKa of substituents bearing nitro and cyano groups. Focusing on B3LYP, eventually remarkable outputs were obtained only when Bondi correction was applied to the complex with two water molecules. Hence, massive outcomes were obtained in foreseeing the trichloro and trifluoro acetic acid pKa. These findings demonstrated that no complex level of theory nor external factor is required to accurately predict carboxylic acids pKa, with MAE well below 0.5 units.
Luminescent Chiral Furanol‐PAHs via Straightforward Ni‐Catalysed Csp2−F Functionalization: Mechanistic Insights into the Scholl Reaction
Authors: Sala Judith , Capdevila Lorena , Berga Cristina , de Aquino Araceli , Rodríguez Laura , Simon Sílvia , Ribas Xavi 
Published: October 2023

AbstractHere we report the stepwise synthesis of new nanographenes (NGs) and polycyclic aromatic hydrocarbons (PAHs) obtained via Scholl ring fusion applied at aromatic homologation compounds, which are obtained through one‐step Ni‐catalysed Csp2−F functionalization. The latter are rapidly accessed valid precursors for the Scholl reaction, and screening of experimental conditions allowed us to describe for the first time furanol‐bearing PAHs. Mechanistic insights are obtained by DFT to rationalize the formation of the furanol PAHs under moderately acidic conditions. All PAHs and NGs synthesized show moderate/weak fluorescent properties, and all PAHs crystallized show some degree of curvature and are obtained as racemic mixtures. Enantiomeric separation by chiral HPLC of one furanol‐bearing PAH allowed the study of their chiroptical CD properties.
Direct Synthesis of N‐formamides by Integrating Reductive Amination of Ketones and Aldehydes with CO2 Fixation in a Metal‐Organic Framework
Authors: Huang Wenyuan , Mei Qingqing , Xu Shaojun , An Bing , He Meng , Li Jiangnan , Chen Yinlin , Han Xue , Luo Tian , Guo Lixia , Hurd Joseph , Lee Daniel , Tillotson Evan , Haigh Sarah J. , Walton Alex , Day Sarah J. , Natrajan Louise S. , Schröder Martin , Yang Sihai 
Published: October 2023

AbstractFormamides are important feedstocks for the manufacture of many fine chemicals. State‐of‐the‐art synthesis of formamides relies on the use of an excess amount of reagents, giving copious waste and thus poor atom‐economy. Here, we report the first example of direct synthesis of N‐formamides by coupling two challenging reactions, namely reductive amination of carbonyl compounds, particularly biomass‐derived aldehydes and ketones, and fixation of CO2 in the presence of H2 over a metal‐organic framework supported ruthenium catalyst, Ru/MFM‐300(Cr). Highly selective production of N‐formamides has been observed for a wide range of carbonyl compounds. Synchrotron X‐ray powder diffraction reveals the presence of strong host‐guest binding interactions via hydrogen bonding and parallel‐displaced π⋅⋅⋅π interactions between the catalyst and adsorbed substrates facilitating the activation of substrates and promoting selectivity to formamides. The use of multifunctional porous catalysts to integrate CO2 utilisation in the synthesis of formamide products will have a significant impact in the sustainable synthesis of feedstock chemicals.
New Methyl Methacrylate Derived Adsorbents – Synthesis, Characterization and Adsorptive Removal of Toxic Organic Compounds
Authors: Wawrzkiewicz Monika , Podkościelna Beata , Podkościelny Przemysław , Gilev Jadranka Blazhevska 
Published: October 2023

AbstractThis study aimed to synthesize polymeric adsorbents by suspension polymerization using methyl methacrylate (MMA) with different crosslinking monomers. Divinylbenzene (DVB) and aliphatic monomers: ethylene glycol dimethacrylate (EGDMA) or N,N′‐methylenebisacrylamide (NN) containing additional amide groups were used. The possibility of using the prepared copolymers (MMA‐NN, MMA‐EGDMA, MMA‐DVB) as adsorbents for the removal of toxic compounds such as dyes (C.I. Acid Red 18 (AR18), C.I. Acid Green 16 (AG16), C.I. Acid Violet 1 (AV1), C.I. Basic Yellow 2 (BY2), C.I. Basic Blue 3 (BB3) and C.I. Basic Red 46 (BR46)) and phenol (PhOH) from dye baths and effluents was evaluated. Preferential adsorption of basic‐type dyes compared to acid‐type dyes or phenol was observed by the polymers. Adsorbent based on MMA‐EGDMA exhibited the highest capacity for investigated dyes and phenol. The pseudo‐second order kinetic model as well as the intraparticle diffusion model can find application in predicting sorption kinetics. Based on the equilibrium sorption data fitted to the Langmuir, Freundlich, Temkin and Dubinin‐Radushkevich model, uptake of BB3, AV1 and PhOH is rather physisorption than chemisorption. The regeneration yield of MMA‐EGDMA does not exceed 60 % using 1 M HCl, 1 M NaCl, and 1 M NaOH in 50 %v/v methanol.
Crystal Structure, Quantum Chemical, Hirshfeld Surface and Molecular Docking of Organic Molecular Salt: 2‐Amino‐5‐Chloropyridinium‐2,4‐Dihydroxybenzoate
Authors: Ponnusamy Kavitha , Madhu Rajkumar , Athianna Muthusamy 
Published: October 2023

AbstractAn organic molecular salt, 2‐amino‐5‐chloropyridinium‐2,4‐dihydroxybenzoate (ACP‐DHB) is synthesized by the slurry method followed by crystallization from methanol. The formation of molecular salt is initially confirmed by1H and13C nuclear magnetic resonance (NMR) spectral data. Single crystal X‐ray diffraction (XRD) analysis shows that the crystal belongs to the monoclinic crystal system with space group, P21/n. Further, the supramolecular assembly involved the extensive network of N+−H···O−and N−H···O hydrogen bonds as well as C‐Cl···O halogen bond. Using UV‐Visible spectral data, the optical band gap is calculated and found to be 4.21 eV. Photoluminescence studies indicate the crystal has blue light emission properties. TG/DTA analysis shows that ACP‐DHB is thermally stable up to 162 °C. The quantum chemical calculations and natural bond analysis (NBO) are performed at B3LYP/6‐311G++ (d,p) basis set using Gaussian 09 software. The relative contributions of various intermolecular connections are discussed using Hirshfeld surface analysis and fingerprint plot illustration. The antibacterial and antifungal activity exhibits better inhibitory capacity against pathogens. Molecular docking revealed that ACP‐DHB efficiently binds with the 1UAG and 5KEE targets and has strong binding ability to the proteins. ADMET factors and Lipinski's rule of five are used to predict drug likeness property.