“XXT完全线上”教学模式在分析化学课程中的实践与思考

本校分析化学教学团队采用学银在线平台(Xueyinonlineplatform)、学习通(Xuexitong)与腾讯会议(Tencent meeting)三结合的"XXT完全线上"教学模式,成功开展了分析化学课程在线教学。该教学模式既充分发挥了已有在线课程资源的作用,又提供了丰富的教学活动。实践证明,"XXT完全线上"教学打破了教与学的时空限制,为有效实施在线教学提供了参考。

C(sp^2)-H/O-H cross-dehydrogenative coupling of quinoxalin-2(1H)-ones with alcohols under visible-light photoredox catalysis

An efficient and practical route to various 3-alkoxylquinoxalin-2(1 H)-ones through visible-light photocatalytic C(sp^2)-H/O-H cross-dehydrogenation coupling of quinoxalin-2(1 H)-ones and alcohols,employing ambient air as an oxidant at room temperature under metal-free conditions,was developed.

Sustainable electrochemical cross‐dehydrogenative coupling of4‐quinolones and diorganyl diselenides

An environmentally friendly method for the synthesis of 3‐organylselenyl quinolones through theelectrochemical cross‐dehydrogenative coupling of 4‐quinolones and diorganyl diselenides wasdeveloped.As a green,atom economic and self‐separating process,the present reaction requiresneither external oxidants nor electrolytes,forming a recyclable catalytic system.

Formation and growth of precipitates in a Mg-7Gd-5Y-1Nd-2Zn-0.5Zr alloy aged at 200℃

Crystal structures,growth characteristics,and transformation of the precipitates in a Mg-7Gd-5Y-1Nd-2Zn-0.5Zr(wt.%)alloy aged at 200℃for various durations were investigated using transmission electron microscopy(TEM)and high-angle annular dark-field scanning transmission electron microscopy(HAADF-STEM).A detailed Mg-Gd type precipitation sequence for Mg-Gd-Y-Nd-Zn alloys was proposed as follows:supersaturated solid solution→solute clusters→zigzag GP zones+β''(I)→β'→β'+protrusions/joints→pre-β_(1)→β_(1)→β.Solute clusters formed in the early stage of aging consisted of one or more rare-earth(RE)/Zn-rich atomic columns with different configura-tions.RE/Zn-rich solute clusters grew into zigzag GP zones andβ''(I)as aging time extending.The paired-zigzag GP zones might grow up to beβ'precipitates directly.In the peak-and plat-aging stages,the number of solute clusters in the matrix decreased until they disappeared,and most existed as zigzag arrays and super hexagons.Protrusions formed at the end ofβ'at an angle of 120°,then grew into joints when two differentβ'variants encountered together.Protrusions/joints comprise zigzag arrays,super-hexagons,β'F,β''(II),β_(T),and hybrid structures rich in solute atoms,and act as catalysts for the growth of theβ'variants.Largerβ'grow by joints consumption while smallerβ'precipitates dissolve to form joints.β_(1)precipitates essentially evolve from pre-β_(1)precipitates,with four-point diamond structures formed by RE/Zn atomic substitution and atomic migration based on the originalα-Mg structure.

Modulated noble metal/2D MOF heterostructures for improved hydrogen storage of MgH_(2)

The conjugation of external species with twodimensional(2D)materials has broad application prospects.In this study,we have explored the potential of noble metal/2D MOF heterostructures in hydrogen storage.Specifically,the MgH_(2)-Ni-MOF@Pd system has shown remarkable hydrogen desorption/sorption performances,starting to liberate hydrogen at 1810C,which is 2300C lower than that of pristine MgH2.Under the catalytic effect of Ni-MOF@Pd,the dehydrogenation apparent activation energy of MgH2 is noticeably decreased from(133.5±17.5)to(34.58±1.87)kJ·moL^(-1),and the hydrogenation apparent activation energy is reduced from(70.41±7.43)to(25.78±4.64)kJ·moL^(-1),which is lowered by 63.4%.The fully-dehydrogenated MgH2-NiMOF@Pd composite rapidly uptakes hydrogen,with 2.62wt%at 100℃and 6.06 wt%at 150℃within 300 s,respectively.The mechanism analysis of MgH2 catalyzed by Ni-MOF@Pd has revealed that the transformation of Mg_2Ni and Mg_2NiH_4 could act as a"hydrogen pump",providing numerous channels for fast diffusion and transport of hydrogen atoms.Moreover,in the dehydrogenation process,the element Pd reacts with MgH_(2)to form the MgPd alloy phase,which makes MgH_(2)take precedence to decompose through the Mg-Pd alloy rather than self-decomposition,further reducing thermal stability and improving de/hydrogenation kinetics.The synergistic effect of Mg-Pd,Mg_2Ni,and the special ultra-thin 2D sheet structure of the additive is the main reason for the good hydrogen storage property of MgH_(2)-Ni-MOF@Pd.Our findings provide inspiration for designing efficient multifunctional additives with unique morphologies to optimize the hydrogen desorption/sorption behaviors of hydrogen storage materials.

Establishment of a leucine-based poly(ester amide)s library with self-anticancer effect as nano-drug carrier for colorectal cancer treatment

Colorectal cancer is a common cancer worldwide.Traditional chemotherapeutic drugs often face limitations such as poor aqueous solubility and high systemic toxicity,which can lead to adverse side effects and limited therapeutic efficacy.In this study,a library of one kind of biodegradable and biocompatible polymer,leucine based-poly(ester amide)s(Leu-PEAs)was developed and utilized as drug carrier.The structure of Leu-PEAs can be tuned to alter their physicochemical properties,enhancing drug loading capacity and delivery efficiency.Leu-PEAs can self-assemble into nanoparticles by nanoprecipitation and load paclitaxel(PTX)with the diameter of~108 nm and PTX loading capacity of~8.5%.PTX-loaded Leu-PEAs nanoparticles(PTX@Leu-PEAs)demonstrated significant inhibition of CT26 cell growth in vitro.In vivo,these nanoparticles exhibited prolonged tumor accumulation and antitumor effects,with no observed toxicity to normal organs.Furthermore,blank Leu-PEAs nanoparticles also showed antitumor effects in vitro and in vivo,which may be attributed to the activation of the mammalian target of rapamycin(m TOR)pathway by leucine.Consequently,this biocompatible Leu-PEAs nano-drug delivery system shows potential as a promising strategy for colorectal cancer treatment,warranting further investigation.

TsCl-promoted sulfonylation of quinoline N-oxides with sodium sulfinates in water

An eco-friendly protocol for the synthesis of various 2-sulfonyl quinolines/pyridines through sulfonylation of heteroaromatic N-oxides with sodium sulfinates in water at ambient temperature under metal-and oxidant-free conditions has been developed.The mild reaction conditions,high reaction efficiency,operational simplicity,short reaction time and remarkable functional-group compatibility make the developed protocol very attractive for the preparation of 2-sulfonyl N-heteroaromatic compounds.

Optimizing hydrogen ad/desorption of Mg-based hydrides for energy-storage applications

Hydrogen energy is expected to be an“ideal fuel”in the era of decarbonization.The discovery,de-velopment,and modification of high-performance hydrogen storage materials are the keys to the fu-ture development of solid-state hydrogen storage and hydrogen energy utilization.Magnesium hydride(MgH_(2)),with its high hydrogen storage capacity,abundant natural reserves,and environmental friend-liness,has been extensively researched.Herein,we briefly summarize the typical structure and hy-drogenation/dehydrogenation reaction mechanism of MgH_(2)and provide a comprehensive overview of strategies to effectively tune the thermodynamics and kinetics of Mg-based materials,such as alloy-ing,nanosizing,the introduction of additives,and composite modification.With substantial efforts,great achievements have been achieved,such as lower absorption/desorption temperatures and better cy-cling stability.Nonetheless,some pivotal issues remain to be addressed,such as unfavorable hydro-genation/dehydrogenation factors,harsh conditions,slow kinetics,incomplete dehydrogenation,low hy-drogen purity,expensive catalysts,and a lack of valid exploration of mechanisms in the hydrogena-tion/dehydrogenation process.Lastly,some future development prospects of MgH_(2)in energy-efficient conversion and storage have been presented,including advanced manufacturing ways,stabilization of nanostructures,the introduction of additives combined with structural modification,and utilization of advanced characterization techniques.

Solvent-dependent selective oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid under neat conditions

An eco-friendly and economical route for the oxidation of 5-hydroxymethylfurfural(HMF) to 2,5-furandicarboxylic acid(FDCA) with atmospheric dioxygen as the sole oxidant under acid-,base-,metal-,and external initiator-free conditions in minimal solvent was reported.In the present reaction,the 1,2-diethoxyethylane has a dual role:reaction medium and free-radical initiato r.The FDCA easily crystallizes during the reaction and was simple purified via recrystallization to provide the pure FDCA.

Stochastic pedestrian avoidance for autonomous vehicles using hybrid reinforcement learning

Ensuring the safety of pedestrians is essential and challenging when autonomous vehicles are involved.Classical pedestrian avoidance strategies cannot handle uncertainty,and learning-based methods lack performance guarantees.In this paper we propose a hybrid reinforcement learning(HRL)approach for autonomous vehicles to safely interact with pedestrians behaving uncertainly.The method integrates the rule-based strategy and reinforcement learning strategy.The confidence of both strategies is evaluated using the data recorded in the training process.Then we design an activation function to select the final policy with higher confidence.In this way,we can guarantee that the final policy performance is not worse than that of the rule-based policy.To demonstrate the effectiveness of the proposed method,we validate it in simulation using an accelerated testing technique to generate stochastic pedestrians.The results indicate that it increases the success rate for pedestrian avoidance to 98.8%,compared with 94.4%of the baseline method.

Sustainable routes for quantitative green selenocyanation of activated alkynes

Most organic reactions require the usage of volatile organic compounds in the synthesis, work-up and purification processes, thus resulting in major environmental pollution and high manufacturing cost. By using cheap biomass lactic acid as the reaction media and catalyst, a sustainable protocol for the synthesis of Z-3-selenocyanatoacrylates and analogues through green selenocyanation of activated alkynes has been achieved. A principal advantage of this protocol is that the usage of organic volatile compounds can be avoided entirely, as the conversion of substrate is almost quantitative or quantitative with a minimal amount of lactic acid employed as reaction media, and the pure products can be conveniently collected through water precipitation.

Visible-light-initiated malic acid-promoted cascade coupling/cyclization of aromatic amines and KSCN to 2-aminobenzothiazoles without photocatalyst

By using ambient air as the oxidant and malic acid as the promoter,a practical method for the preparation of 2-aminobenzothiazoles through visible-light-initiated cascade reaction of aromatic amines and KSCN in eco-friendly bis(methoxypropy)ether under metal-,hazardous additive-,photocatalyst-free conditions was established.

The concept of dual roles design in clean organic preparation

Herein we summarized some clean preparation examples to emphasize the concept of dual roles design(or named as "two birds one stone strategy") in green and sustainable chemistry.In those examples,the reactants and/or solvent play dual roles rendering a cleaner organic preparation process.Consequently,both the chemical waste and manufacturing cost could be reduced.

Driving Space for Autonomous Vehicles

Driving space for autonomous vehicles(AVs)is a simplified representation of real driving environments that helps facilitate driving decision processes.Existing literatures present numerous methods for constructing driving spaces,which is a fundamental step in AV development.This study reviews the existing researches to gain a more systematic understanding of driving space and focuses on two questions:how to reconstruct the driving environment,and how to make driving decisions within the constructed driving space.Furthermore,the advantages and disadvantages of different types of driving space are analyzed.The study provides further understanding of the relationship between perception and decision-making and gives insight into direction of future research on driving space of AVs.

Visible-light-initiated tandem synthesis of difluoromethylated oxindoles in 2-MeTHF under additive-,metal catalyst-,external photosensitizer-free and mild conditions

An efficient and eco-friendly protocol for synthesizing difluoromethylated oxindoles through a visiblelight induced one-pot tandem reaction of N-arylacrylamides,difluoroacetic acid and Ph I(OAc)_(2)was developed.This reaction proceeded in the absence of any additive,base,metal-catalyst and external photosensitizer,using cheap and easily available CHF_(2)CO_(2)H as the difluoromethylation reagent and bulk biomass-derived 2-Me THF as the sole solvent.26 Examples of N-arylacrylamide substrates were investigated,and all of them successfully underwent difluoromethylation to deliver the target products in good to excellent yields.

A novel two-dimensional nanoheterojunction via facilitating electron–hole pairs separation for synergistic tumor phototherapy and immunotherapy

Nanomaterial-mediated phototherapy in tumor treatment has been developed rapidly in the past few years due to its noninvasive character.However,the low energy conversion efficiency and high recombination rate of the photo-triggered electron–hole pairs of single nano-agent limit the phototherapy efficiency.Herein,we constructed a novel two-dimensional nanoheterojunction MoS_(2)-Ti_(3)C_(2)(MT),which allowed a high photothermal conversion efficiency(59.1%)as well as an effective separation of photo-triggered electron–hole pairs for reactive oxygen species(ROS)generation under single 808 nm laser irradiation.Upon the modification of the mitochondrial targeted molecule(3-proxycarboxylic)triphenyl phosphine bromide(TPP)and 4T1 cell membrane,m@MoS_(2)-Ti_(3)C_(2)/TPP(m@MTT)could effectively target to the tumor cell and further locate to the mitochondria to amplify tumor-specific oxidative stress,which not merely effectively inhibits the local tumor growth but also induces tumor immunogenic cell death(ICD)for activating antitumor immune response.Additionally,cytosine guanine dinucleotide(CPG),as a Toll-like receptor 9(TLR9)agonist,was further introduced to the system to boost adaptive immune responses,resulting in improved level of cytotoxic T cells as well as a decrease in the number of regulatory T cells.In vivo antitumor mechanism studies demonstrated that not only the primary and distant tumors in 4T1 bearing-tumor mice model were significantly inhibited,but also the lung metastasis of tumor was effectively suppressed.Therefore,this work revealed the ROS generation mechanism of MT nanoheterojunction and provided a novel strategy to fabricate a biomedically applicable MT nanoheterojunction for tumor treatment.

An Enzyme-Free Amperometric Sensor Based on Self-Assembling Ferrocene-Conjugated Oligopeptide for Specific Determination of L-Arginine

Main observation and conclusion An enzyme-free amperometric sensor based on a heptadecapeptide possessing an electroactive ferrocene(Fc)linker as ferrocene-Gly-Gly-Gly-Gly-Phe-Gly-His-Ile-His-Glu-Gly-Tyr-Gly-Gly-Gly-Gly-Lys-(CH_(2))_(4)-dithiocyclopentane self-assembled on gold substrate was designed and fabricated for specific determination of L-arginine(L-Arg).The detection mechanism is based on conformational change of surface-immobilized peptide induced by the target L-Arg,which was confirmed via SEM,TEM,AFM,XPS,and SPR studies.The binding affinity and the recognition feasibility of immobilized specific and non-specific peptides were also assessed using electrochemical impedance spectroscopy(EIS),cyclic voltammetry(CV),and differential pulse voltammetry(DPV).The proposed method can serve as“signal-on”sensor for detection of L-Arg down to 31 pmol/L with broad linear range(0.0001 to 10μmol/L).Furthermore,the Fc-conjugated specific peptide sensor was successfully applied to the determination of L-Arg in pig serums with a recovery rate of 97.5%—106.9%,and its test results are in good agreement with that of chromatographic instrument,evidencing that the oligopeptide-based sensor can be served as a simple and enzyme-free biosensing platform towards L-Arg for future application.

Clean preparation of S-thiocarbamates with in situ generated hydroxide in 2-methyltetrahydrofuran

A simple and clean protocol for the synthesis of various alkyl and(hetero)aryl S-thiocarbamates was established.The usage of in situ generated hydroxide as both an oxygen source and hydrogen source as well as biomass-derived 2-methyltetrahydrofuran as a green reaction medium,the avoidance of phosphorus-containing reductant,and the generation of harmless water and nitrogen as the sideproducts have given the present method atom-economy and environmental friendliness.

Adaptive H∞control of polynomial Hamiltonian systems via symbolic computation:controller parameterisation

This paper deals with controller parameterisation method of adaptive H∞control for polynomial Hamiltonian systems(PHSs)with disturbances and unknown parameters.We design a simplified controller with a set of tuning parameters which can guarantee that the systems are adaptive H∞stable by using Hamiltonian function method.Then,a method for solving the set of tuning parameters of the controller with symbolic computation is presented.The proposed parameterisation method avoids solving Hamilton–Jacobi–Issacs(HJI)equations and the obtained controller is easier as compared to some existing ones.Simulation example shows that the controller is effective as it can optimise adaptive H∞control by adjusting tuning parameters.All these results are expected to be of use in the study of adaptive H∞control for nonlinear systems with disturbances and unknown parameters.

Metal-free C3-alkoxycarbonylation of quinoxalin-2(1H)-ones with carbazates as ecofriendly ester sources

Quinoxaline-3-carboxylates and analogues are prevalent key structural motifs in bioactive natural products and synthetic drugs.However, the practical protocol for preparation of these motifs from simple raw materials under mild conditions remains rare. In this article, we report a facile protocol for the efficient preparation of various quinoxaline-3-carbonyl compounds(30 examples,63%–92%) through oxidation coupling of quinoxalin-2(1H)-ones with readily available carbazates(or acyl hydrazines) in the presence of K_2S_2O_8 as an oxidant in metal-and base-free conditions. When tert-butyl carbazate was used as the coupling reagent,the decarboxylation product 3-(tert-butyl)-1-methylquinoxalin-2(1H)-one was obtained. The application of this process into a gram-scale synthesis can be easily accomplished. Mechanistic investigations reveal that the functionalization of quinoxalin-2(1H)-ones via a free-radical pathway.