bluuebunny/crossref_metadata_2025_split huggingface dataset:
A universal free energy relationship for both hard and soft radical addition in water
Authors: Nolte Tom M. , Hendriks A. Jan , Novák Laurie A. , Peijnenburg Willie J. G. M. 
Published: January 2022

AbstractPrioritization of (eco)toxicological risks and technological endpoints among 100,000+ potential substances, conditions and mechanisms requires computationally ‘inexpensive’ and accurate tools to ‘screen’ reactivity and identify reaction products. Such prediction tools are very scarce. Left unresolved, charge‐transfer and hydration complicate predictions. Based on experimental reaction of radicals (3O2, CH3•, CO3•− etc.) with organic substrates, we hypothesized that a universal linear free energy relationship (LFER) can rationalize these reactions to accurately predict addition rates.We calculated free energies of forming charge‐separated intermediates from explicit descriptions of addition reaction products. We combined these energies, via a thermodynamic cycle, with electron transfer energies to calculate product formation energies. All energies include consideration of hydration effects by water. We ascribe feasibilities of ‘hard’ (ionic) and ‘soft’ (covalent) mechanisms to the relevance of the charge‐separated intermediate.Analysis shows that activation energies effectively relate to a combination of product formation energies and charge‐separation energies. The relative importance of these is determined by a mixing parameter, which is mostly constant for a given radical (substrate). Via the Eyring equation, our universal LFER explains up to 94% of the variance in data for rate constants. Prediction error is a factor 5 (2 SD), only slightly larger than variation in experimentation, particularly sensitive to varying reaction conditions.Minimal parametrization ensures that our new framework for calculating reactivity of radical addition is accurate, robust and with satisfactory rational. Calculation time for 100 reactions is <1 h on a standard desktop PC. In anticipation of underpinning with an even wider range of reagents, this ‘inexpensive’ calculus can more easily assess a greater domain of structures and extrapolate to new structures. This helps to better assess and select favourable non‐toxic, environmentally friendly and technologically superior chemical (sub)structures.
Sleep disruption and its contributing factors in Chinese survivors of childhood cancer: A cross‐sectional study
Authors: Ho K. Y. , Lam Katherine K. W. , Xia W. , Chiu S. Y. , Chan Godfrey C. F. 
Published: January 2022

AbstractObjectivesThis study provided information about sleep disruption, particularly its prevalence and severity among Hong Kong Chinese childhood cancer survivors. Additionally, we identified the factors influencing sleep disruption and explored how fatigue, depressive symptoms and physical activity (PA) affect sleep disruption.MethodsFour hundred two survivors 6–18 years old and 50 age‐ and gender‐matched healthy counterparts were assessed for depressive symptoms, fatigue, PA and subjective sleep quality. Demographic and clinical information were collected. Multiple logistic regression analyses were conducted to identify any factors contributing to poor sleep.ResultsMean scores of depressive symptoms, fatigue for children and that for adolescents, and PA in survivors were 16.1 (SD = 11.1), 24.6 (SD = 10.3), 27.7 (SD = 7.8), and 3.08 (SD = 2.9), respectively. 44.8% of the survivors were poor sleepers, which was more that in healthy counterparts. The three most common sleep problem were prolonged sleep latency (31.9%), daytime dysfunction (23.4%), and sleep disturbance (22.9%). The time since last treatment (children: AOR = 0.54, 95% CI = 0.30–0.96, p = 0.04; adolescents: AOR = 0.80, 95% CI = 0.70–0.92, p < 0.01) and PA levels (children: AOR = 0.46, 95% CI = 0.260–0.82, p = 0.01; adolescents: AOR = 0.70, 95% CI = 0.49–0.98, p = 0.04) were negatively associated with sleep disruption, while depressive symptoms (children: AOR = 1.31, 95% CI = 1.04–1.64, p = 0.02; adolescents: AOR = 1.07, 95% CI = 1.01–1.13, p = 0.03), fatigue (children: AOR = 1.15, 95% CI = 1.00–1.31, p = 0.04; adolescents: AOR = 1.08, 95% CI = 1.02–1.15, p = 0.01), number of treatment received (children: AOR = 16.56, 95% CI = 1.27–216.82, p = 0.03; adolescents: AOR = 7.30, 95% CI = 2.36–22.56, p < 0.01), and co‐sleeping (children: AOR = 29.19, 95% CI = 1.65–511.57, p = 0.02; adolescents: AOR = 4.63, 95% CI = 1.22–17.61, p = 0.02) were positively associated with sleep disruption.ConclusionPhysical activity made the largest contribution to reduce sleep disruption. It is crucial to advocate for the adoption and maintenance of PA in survivorship.
Mg substitution in zinc selenide: Enhanced optoelectronic and thermoelectric performance
Authors: Abdelhadi Sofiane , Abid Hamza , Bensaid Djillali 
Published: January 2022

AbstractIn this research, we applied a full‐potential linearized muffin‐tin orbital (FP‐LMTO) method to investigate the optoelectronic properties such as electronic structures and optical properties in the first phase, and then we try to improve the thermoelectric performance through the substitution by an element alkaline earth metal (Mg). The analysis of band structure and optical properties indicate a semiconductors character with wide directly band gap along alkaline earth metal element (Mg) substitution. The present comprehensive analyses of electronic and optical properties of these alloys predict that they could be useful for optoelectronic devices. Thermal parameters such as thermal conductivity and power factor show good improvement for very small substitutions; this tells me that our material has a ZT close to promising alloys in thermoelectric applications. This result encourages going deep in order to obtain good thermoelectric performance at high temperature which requires adjusting the concentration of carriers, thermal conductance and the amount of Mg. At the end, Mg doped ZnSe is a favorable material for both optoelectronic and thermoelectric application.
Dynamic event‐triggered fixed‐time adaptive fuzzy control of nonstrict‐feedback switched nonlinear systems
Authors: Wang Fenglan , Long Lijun 
Published: January 2022

AbstractIn this paper, a dynamic event‐triggered fixed‐time adaptive fuzzy control method is set up to solve the tracking problem for a type of nonstrict‐feedback switched nonlinear systems with asymmetric tracking error constraints. The proposed method constructs different event‐triggered adaptive fuzzy controllers for different subsystems together with switched update laws and a switching dynamic event‐triggering mechanism (DETM). Under this switching DETM, the difficulty caused by asynchronous switching between candidate controllers of subsystems and subsystems is effectively overcome, and the known limitations on maximum asynchronous time in the existing literature are not needed. Meanwhile, Zeno behavior is avoided by deriving a strictly positive lower bound of interevent times. It is guaranteed that the asymmetric tracking error constraints are never violated and the tracking error can converge to a small neighborhood of origin in a fixed‐time under arbitrary switchings. Finally, the feasibility of the derived theoretical results is demonstrated by employing a numerical example and a switched Chua's Circuit system.
Learning event‐triggered control based on evolving data‐driven fuzzy granular models
Authors: Cordovil Luiz A. Q. , Coutinho Pedro H. S. , Bessa Iury , Peixoto Márcia L. C. , Palhares Reinaldo Martínez 
Published: January 2022

AbstractThis article proposes a data‐stream‐driven event‐triggered control strategy using evolving fuzzy models learned by granulation of input–output samples of nonlinear systems with unknown time‐varying dynamics. The evolving fuzzy model is obtained online from a data stream ensuring data coverage based on the principle of justifiable granularity and controlled by an event‐triggering learning mechanism dependent on the model accuracy. This evolving fuzzy model is used to design event‐triggered fuzzy controller to stabilize networked control systems while reducing the used communication resources. The event‐triggered learning mechanism is employed to determine the instants in which the event‐triggered fuzzy controller should be redesigned. Numerical examples illustrate the effectiveness of the proposed learning event‐triggered fuzzy control algorithm.
Parameter identification and state estimation for a diabetic glucose‐insulin model via an adaptive observer
Authors: Franco Roberto , Ríos Héctor , Ferreira de Loza Alejandra , Cassany Louis , Gucik‐Derigny David , Cieslak Jérôme , Henry David 
Published: January 2022

AbstractIn this article, an adaptive observer is designed for patients with Type 1 Diabetes Mellitus. The adaptive observer, synthesized using the so‐called Bergman's Minimal Model, simultaneously estimates the states and the parameter corresponding to the insulin‐independent glucose disappearance rate. The adaptive observer deals with parameter uncertainties, whereas the food intake is regarded as an external disturbance. The adaptive observer relies on intravenous glucose measurements. The state estimation error converges to a neighborhood of the origin despite the effects of the external disturbances and uncertainties, while the parameter estimation error converges in a fixed time to a neighborhood of the origin. The adaptive observer synthesis is given by a constructive method based on linear matrix inequalities. Simulation results show the feasibility of the proposed scheme. Moreover, the approach is validated in UVA/Padova metabolic simulator for ten in silico adult patients.
Preparation of Heteroatom‐Doped Carbon Materials and Applications in Selective Hydrogenation
Authors: Zhang Qunfeng , Zhang Deshuo , Zhou Yuan , Qian Jiacheng , Wen Xiaoyu , Jiang Piaopiao , Ma Lei , Lu Chunshan , Feng Feng , Li Xiaonian 
Published: January 2022

AbstractHeteroatom‐doping of carbon materials has gained much attention recent decades since it was believed to be a brilliant strategy to endow carbon with enhanced physical and chemical properties. In addition, the doped carbon has been frequently employed in various fields such as supercapacitors, batteries, catalytic hydrogenation reactions due to its unique structure and superior features, among which selective hydrogenation is an essential procedure during organic synthesis and has wide industrial applications. It is proved that the incorporation of heteroatoms could have a great effect on the original carbon, such as charge distribution and surface defects, which could further influence the electronic effect and physical interaction between carbon carrier and supported metal, thereby enhance its catalytic performance in hydrogenation reactions. Herein, we briefly reviewed recent progress in the effect of heteroatoms on carbon properties. Meanwhile, the synthesis strategies of doped‐carbon and the application of these catalysts in series of hydrogenation reactions were also summarized.
Influence of Pd‐Doping on The Efficiency of In2O3/ZrO2 Catalysts Used for Hydrogenating Dimethyl Oxalate to Ethanol
Authors: Xue Haodong , Qin Siqian , Wang Xue , Zhang Chuancai , Wang Denghao , Dai Bin 
Published: January 2022

AbstractA co‐precipitation method followed by an impregnation method was used to synthesize the xPd‐In2O3/ZrO2 catalysts that could be used for the hydrogenation of dimethyl oxalate to ethanol. The results indicated that xPd‐In2O3/ZrO2 exhibited excellent catalytic activity during the hydrogenation of dimethyl oxalate to ethanol. It was found that Pd−doping could improve the performance of the catalysts. 100 % conversion and 84 % ethanol selectivity could be achieved using the 0.5 % Pd‐In2O3/ZrO2 catalyst. In‐depth charact‐erization of the xPd‐In2O3/ZrO2 catalyst revealed the occurrence of hydrogen spillover and the formation of oxygen vacancies on the surface of the catalyst. The improvement in the catalytic activity can be attributed to the increase of activated hydrogen concentration during the process of hydrogen spillover in the presence of Pd and the enhancement of activation capacity (toward dimethyl oxalate) of the catalyst caused by the formation of oxygen vacancies.
Mechanism of Rhubarb for Diabetic Kidney Disease through the AMPK/NF‐κB Signaling Pathway Based on Network Pharmacology
Authors: Luo Jinli , Piao Chunli , Jin De , Wang Li , Zhao Xiaohua , Lian Fengmei , Tong Xiaolin 
Published: January 2022

AbstractRhubarb (Da‐huang in pinyin, Radix Rhei Et Rhizome in pharmaceutical name) is a heat‐clearing and laxative herbal medicine, which is widely used to treat diabetic kidney disease in China. The study aims to decrypt the underlying mechanisms of the treatment of diabetic kidney disease using a systems pharmacology approach. Active compounds and corresponding potential therapeutic targets were harvested by utilizing the database of TCMSP. DKD targets were adopted from DrugBank, OMIM, TTD, and GAD databases. Then a network of Rhubarb‐ compounds ‐ target ‐ DKD network was harvested. The PPI network was then generated by the String database and subjected to Cytoscape software to harvest major and core targets network by topological analysis. Genes from the core targets network were further subjected to GO and KEGG enrichment analysis to figure out potential targeting pathways. Human podocyte cells (HPC) were used to further investigate the mechanism of against DKD. A total of 6 active ingredients and 271 targets of Rhubarb were picked out. 11 cellular biological processes and 18 pathways of mostly associated with inflammatory response, apoptosis, fibrosis, and peripheral circulation. Moreover, experimental validation suggests that Rhubarb increased cell viability. Rhubarb extract significantly suppressed the expression of NF‐kappa B, Bcl‐2, Caspase‐3, and Cleaved Caspase‐3, promoted the expression of AMPK and Bax, and decreased the release of cytokines. Rhubarb could alleviate DKD via the molecular mechanisms predicted by network pharmacology.
A Facile Approach to Benzosultam‐fused 4‐Imidazolidinone Derivatives from N‐Sulfonyl Ketimine and α‐Halogenated Hydroxamates
Authors: Lan Wenjie , Lei Rong‐chao , Luo Jiayu , Qin Zhaohai , Fu Bin , Xie Lei 
Published: January 2022

AbstractThe novel benzosultam‐fused 4‐imidazolidinone scaffold was constructed by a concise [3+2] annulation reaction of α‐halogenated hydroxamates and N‐sulfonyl ketimine for the first time. The transformation proceeded smoothly under mild and transition‐metal‐free conditions in moderate to excellent yields (up to 95 %). Moreover the annulation products are potentially useful and promising for medicinal research.
Chemoselectivity in the Transannulaction of 1,2,3‐Thiadiazoles and Alk‐2‐enenitriles: Specific Synthesis of 3‐(Alk‐1‐enyl)isothiazoles
Authors: Wu Qiuyue , Chen Ning , Xu Jiaxi 
Published: January 2022

Abstract1,2,3‐Thiadiazoles are precursors of thioacylcarbenes and thioketenes and show various reactions with unsaturated compounds. The rhodium‐catalyzed reactions of 1,2,3‐thiadiazoles and alk‐2‐enenitriles, including alkyl, aryl, and heteroaryl acrylonitriles, have been investigated, showing chemospecific reactivity to generate 3‐vinylisothiazole derivatives via the (3+2) transannulation between the cyano group of alk‐2‐enenitriles and generated thioacylcarbenes. (Z)‐Cinnamonitriles are less active than (E)‐cinnamonitriles due to the strong coordination of the (Z)‐C=C bond and the Rh catalyst. The current reaction provides a method for the synthesis of 3‐vinylisothiazole derivatives.
Interactions of a Ruthenium‐Ketoprofen Compound with Human Serum Albumin and DNA: Insights from Spectrophotometric Titrations and Molecular Docking Calculations
Authors: Sarmento Caroline O. , Pinheiro Bruno F. A. , Abrahão Josielle , Chaves Otávio A. , Moreira Mariete B. , Nikolaou Sofia 
Published: January 2022

AbstractThe compound [Ru2O(keto)2(py)6](PF6)2, keto=ketoprofen and py=pyridine, interacts with calf thymus‐DNA with Kb=1.08×104 M−1. It efficiently quenches HSA fluorescence in different temperatures, with Ksv values in the 104–105 M−1 range, both by dynamic and static mechanisms. The data provided by the double logarithmic and van't Hoff approximations indicated a moderate (Kb≈104 M−1) and spontaneous (ΔG<0) interaction, being enthalpically driven (ΔH=−27.1 kJ mol−1 and ΔS=−5.3 J mol−1 K−1). Molecular docking calculations confirmed that the binuclear compound interacts with HSA more strongly than with DNA. The occurrence of a high contribution from electrostatic forces was observed, fully consistent with the bicationic nature of [Ru2O(keto)2(py)6](PF6)2. The molecular docking results also revealed that the interaction occurs in an external subdomain, explaining the lack of significant conformational changes in the protein, as probed by circular dichroism spectra.
Pickering High Internal Phase Emulsions Templated CoOx−HPC Loading Bimetallic AuPd Nanoparticles for Catalytic Oxidation of 5‐Hydroxymethylfurfural to 2, 5‐Furan Dicarboxylic
Authors: Guan Wen , Chen Chen , Li Bing , Chen Yao , Wei Yanan , Cao Yu , Wang Fang , Yan Yongsheng , Liu Bing , Zhang Yunlei 
Published: January 2022

AbstractThe supported bimetallic AuPd nanoparticles hold great promise for the selective oxidation of 5‐hydroxymethylfurfural (HMF) to 2, 5‐furan dicarboxylic acid (FDCA), a substitute for petroleum derivative terephthalic acid (TPA). Herein, by combining a versatile Pickering high internal phase emulsions (HIPEs) template with subsequent carbonization process, cobalt‐based hierarchical porous carbon (CoOx−HPC) support was obtained. After loading bimetallic AuPd nanoparticles through the sol‐gel method, AuPd/CoOx−HPC catalyst was successfully synthesized. By changing the Pickering HIPEs parameters, carbonization temperature, the porous structure and cobalt valence of as‐synthesized catalyst can be adjusted. The obtained catalysts were systematically characterized by SEM, TEM, N2 adsorption‐desorption, XRD, XPS, and TGA. Benefiting from the synergistic effects of the high porosity of CoOx−HPC support and efficient AuPd nanoparticles, tandem oxidation of HMF to FDCA can be carried out in the water. We have clarified that the catalysts with various cobalt valence states showed superior performance, and the highest FDCA yield of 97.2 % will be obtained under the optimal reaction conditions. Meanwhile, the kinetics study indicated that the oxidation of FFCA to FDCA was the rate‐determining step. Moreover, the AuPd/CoOx−HPC catalyst revealed excellent stability in HMF oxidation during four cycles. The experimental results demonstrated that as‐prepared AuPd/CoOx−HPC catalysts are efficient towards FDCA production from the selective oxidation of HMF.
The Aldol Reaction of α‐Ketoamide with α,β‐Unsaturated Ketone in KOH Aqueous Medium
Authors: Qin Xin , Wu Chaofei , Lu Fanyun , Wang Zhan‐Yong , Jiang Jun , Liu Hongxin 
Published: January 2022

AbstractHerein, we report for the first time the aldol reaction of a wide range of α‐ketoamide with α,β‐unsaturated ketone via the activation of potassium hydroxide in aqueous medium. The protocol provides a straightforward and atom‐efficient strategy for the synthesis of a new family of multifunctional α‐hydroxy amides contain α,β‐unsaturated ketone group from easily accessible substituted α‐ketoamide and α,β‐unsaturated ketone. The reaction features mild reaction conditions, green solvent, one of which is quaternary carbon substitution. The method can accommodate various substituents and substitution patterns, afford the products up to 95 % yields.
DNA‐Gated N‐CDs@SiO2 Nanoparticles‐Based Biosensor for MUC1 Detection
Authors: Liu Yuhong , Liu Xuan , Liu Huaxiao , Wang Jingzhi , Zhang Yawen , Zhao Wenbo , Zhou Jiahong 
Published: January 2022

AbstractThe ultrasensitive detection of mucin1 (MUC1), a typical breast cancer marker, is of great significance for the diagnosis of breast cancer. Here, a biosensor based on DNA‐gated nitrogen‐doped carbon quantum dots‐loaded hollow mesoporous silica nanoparticles (DNA‐gated N‐CDs@SiO2 NPs) for highly sensitive detection of MUC1 were reported. The preparation process and properties of DNA‐gated N‐CDs@SiO2 NPs were characterized in detail. Results of experiments of detection of MUC1 and cell imaging indicate that the biosensor with MUC1‐specific DNA sequence is beneficial for selective detection of MUC1 by MUC1‐triggered unlocking of DNA gate and controlled release of N‐CDs. The biosensor exhibits satisfactory results with a low detection limit of 10 nM and good specificity, as well as MUC1‐positive cell imaging performance, demonstrating the potential for MUC1 detection, which provides a new method for early screening and diagnosis of breast cancer diseases.
Green Biphasic Synthesis, X‐Ray Diffraction Structure and Conformational Analysis of O‐Glycosylmethyl Isoxazoles: Potential Substrates of GLUT‐1 Glucose Transporter.
Authors: Le Pors Macarena S. , Barri Ivan A. , Riafrecha Leonardo E. , Echeverría Gustavo A. , Piro Oscar E. , Colinas Pedro A. 
Published: January 2022

AbstractAn efficient synthesis of new 1‐O‐β‐glycosylmethyl isoxazoles is described. The title compounds are obtained by cycloaddition of nitrile oxides generated in situ in 2‐MeTHF/sodium hypochlorite solution. The developed approach provides the first use of this green methodology to prepare isoxazole derivatives. X‐ray diffraction structure and conformational analysis in solution show that glycosyl isoxazoles possess the structural features required to be substrates of GLUT‐1.
One‐Pot Reductive Amination of Aromatic Aldehydes in [Et3NH][HSO4] using Sodium Borohydride and A Mechanistic Investigation using Computational Method
Authors: Narvariya Rajrani , Gupta Shivangi , Jain Archana , Rawal Parveen , Gupta Puneet , Panda Tarun K. 
Published: January 2022

AbstractThe reductive amination of aromatic aldehydes and aromatic amines, performed in the Brønsted acidic ionic liquid [Et3NH][HSO4], using sodium borohydride as a reducing agent is reported. In this protocol, the ionic liquid plays a crucial role in efficiently converting aromatic aldehydes to amines in excellent yields, without the formation of side products. In the presence of [Et3NH][HSO4], the imine was generated in situ from the reaction between the aromatic aldehydes and aromatic amines, and underwent smooth reduction with sodium borohydride. This one‐pot synthesis is practically simple and sustainable. The catalyst [Et3NH][HSO4] also has a demonstrably wide applicability, in that it can be used with a variety of aromatic aldehydes and aromatic amines substituted by various electron‐withdrawing and electron‐donating groups. The role of IL [Et3NH][HSO4] in catalytic reductive amination is validated with the help of density functional theory (DFT)‐based computational studies.