Synthesis of Polysubstituted 1,4-Dihydropyridines via Four-component Reactions of Arylamine,Acetylenedicarboxylate, Aromatic Aldehyde and Ethyl Acetoacetate

An efficient synthetic protocol for the 1,4-diaryl-1,4-dihydropyridines was developed via the domino four-component reaction of arylamine,acetylenedicarboxylate,aromatic aldehyde and ethyl acetoacetate.The reaction mechanism involves the formation of β-enamino ester and its sequential Michael addition to arylidene acetoacetate.

Synthesis of 2,4-Diarylcyclooctenopyridines with One-pot Four-component Reactions

An efficient one-pot four-component reaction has been developed for the synthesis of 2,4-diarylcyclooctenopyridines, in moderate yields. This route is an effective modified two-step synthesis of Krohnke pyridine and involves a four-component tandem reaction of pyridinium bromide with aromatic aldehydes and cyclooctanone in a system of NHaOAc/HOAc under microwave irradiation.

Search for New Three-, Four-Component Petasis, Passerini, Hantzsch, Kabachnic-Fields, Ugi Reactions with Organic Compounds of Phosphorus, Arsenic, Antimony and Bismuth

It is discovered a new three-, four-component Petasis, Passerini, Hantzsch, Kabachnic-Fields, Ugi reactions with of arsine, stibine and bismuthine in organometallic chemistry. Modifications were replaced to a nitrogen atom of classical reactions of atoms of phosphorus, arsenic, antimony and bismuth. It has been proposed a new mechanism for possible reactions.

Solid-phase Synthesis of PNA Monomer by Ugi Four-component Condensation Reaction

Peptide nucleic acids (PNA) oligomers were synthesized in most cases by peptide synthesis from N-protected monomers. In this work a new method of obtaining PNA monomer by Ugi four-component condensation reaction was tested by solid-phase synthesis. The Fmoc protected PNA monomer was build up with thymin-1-yl acetic acid, 3-methylbutyl aldehyde, Fmoc protected aminoethyl isocyanide and Gly-Wang resin.

“Buckets effect”in the kinetics of electrocatalytic reactions

In this study,we systematically investigated the effect of proton concentration on the kinetics of the oxygen reduction reaction(ORR)on Pt(111)in acidic solutions.Experimental results demonstrate a rectangular hyperbolic relationship,i.e.,the ORR current excluding the effect of other variables increases with proton concentration and then tends to a constant value.We consider that this is caused by the limitation of ORR kinetics by the trace oxygen concentration in the solution,which determines the upper limit of ORR kinetics.A model of effective concentration is further proposed for rectangular hyperbolic relationships:when the reactant concentration is high enough to reach a critical saturation concentration,the effective reactant concentration will become a constant value.This could be due to the limited concentration of a certain reactant for reactions involving more than one reactant or the limited number of active sites available on the catalyst.Our study provides new insights into the kinetics of electrocatalytic reactions,and it is important for the proper evaluation of catalyst activity and the study of structureperformance relationships.

Possibilities for the synthesis of superheavy element Z=121 in fusion reactions

Based on the dinuclear system model,the calculated evaporation residue cross sections matched well with the current experimental results.The synthesis of superheavy elements Z=121 was systematically studied through combinations of stable projectiles with Z=21-30 and targets with half-lives exceeding 50 d.The influence of mass asymmetry and isotopic dependence on the projectile and target nuclei was investigated in detail.The reactions^(254)Es(^(46)Ti,3n)^(297)121 and^(252)Es(^(46)Ti,3n)^(295)121 were found to be experimentally feasible for synthesizing superheavy element Z=121,with maximal evaporation residue cross sections of 6.619 and 4.123 fb at 219.9 and 223.9 MeV,respectively.

Petrology of Spinel-Lherzolite Xenoliths from Mazéléand Others Northen Xenoliths Localities of Cameroon Volcanic Line: Exchange Reactions and Equilibrium State

The alkaline volcanism of the Cameroon Volcanic Line in its northern domain has raised many fresh enclaves of peridotites. The samples selected come from five (05) different localities (Liri, in the plateau of Kapsiki, Mazélé in the NE of Ngaoundéré, Tello and Ganguiré in the SE of Ngaoundéré and Likok, locality located in the west of Ngaoundé). The peridotite enclaves of the above localities show restricted mineralogical variation. Most are four-phase spinel-lherzolites, indicating that this is the main lithology that forms the lithospheric mantle below the shallow zone. No traces of garnet or primary plagioclase were detected, which strongly limits the depth range from which the rock fragments were sampled. The textures and the wide equilibrium temperatures (884˚C - 1115˚C) indicate also entrainment of lherzolite xenoliths from shallow depths within the lithosphere and the presence of mantle diapirism. The exchange reactions and equilibrium state established in this work make it possible to characterize the chemical composition of the upper mantle of each region and test the equilibrium state of the phases between them. Variations of major oxides and incompatible elemental concentrations in clinopyroxene indicate a primary control by partial melting. The absence of typical “metasomatic” minerals, low equilibration temperatures and enriched LREE patterns indicate that the upper mantle below septentrional crust of Cameroun underwent an event of cryptic metasomatic enrichment prior to partial melting. The distinctive chemical features, LREE enrichment, strong U, Ce and Pr, depletion relative to Ba, Nb, La, Pb, and T, fractionation of Zr and Hf and therefore ligh high Zr/Hf ratio, low La/Yb, Nb/La and Ti/Eu are all results of interaction of refractory peridotite residues with carbonatite melts.

Cation effects in electrocatalytic reduction reactions:Recent advances

Electrocatalytic reduction reactions,powered by clean energy sources such as solar energy and wind,offer a sustainable method for converting inexpensive feedstocks(e.g.,CO_(2),N_(2)/NO_(x),organics,and O_(2))into high-value-added chemicals or fuels.The design and modification of electrocatalysts have been widely implemented to improve their performance in these reactions.However,bottle-necks are encountered,making it challenging to further improve performance through catalyst development alone.Recently,cations in the electrolyte have emerged as critical factors for tuning both the activity and product selectivity of reduction reactions.This review summarizes recent advances in understanding the role of cation effects in electrocatalytic reduction reactions.First,we introduce the mechanisms underlying cation effects.We then provide a comprehensive overview of their application in electroreduction reactions.Characterization techniques and theoretical calcula-tion methods for studying cation effects are also discussed.Finally,we address remaining challeng-es and future perspectives in this field.We hope that this review offers fundamental insights and design guidance for utilizing cation effects,thereby advancing their development.

Why Don’t We Adequately Identify and Manage Adverse Drug Reactions despite Having the Needed Information?

Importance/Objective: Adverse Drug Reactions (ADRs) are unavoidable, but recognizing and addressing ADRs early can improve wellness and prevent permanent injury. We suggest that available medical information and digital/electronic methods could be used to manage this major healthcare problem for individual patients in real time. Methods: We searched the available digital applications and three literature databases using the medical subject heading terms, adverse drug reaction reporting systems or management, filtered by clinical trial or systemic reviews, to detect publications with data about ADR identification and management approaches. We reviewed the reports that had abstract or summary data or proposed or implemented methods or systems with potential to identify or manage ADRs in clinical settings. Results: The vast majority of the 481 reports used retrospectively collected data for groups of patients or were limited to surveying one population group or class of medication. The reports showed potential and definite associations of ADRs for specific drugs and problems, mostly, but not exclusively, for patients in hospitals and nursing homes. No reports described complete methods to collect comprehensive data on ADRs for individual patients in a healthcare system. The digital applications have ADR information, but all are too cumbersome or incomplete for use in active clinical settings. Several studies suggested that providing information about potential ADRs to clinicians can reduce these problems. Conclusion and Relevance: Although investigators and government agencies agree with the need, there is no comprehensive ADR management program in current use. Informing the patient’s healthcare practitioners of potential ADRs at the point of service has the potential for reduction of these complications, which should improve healthcare and reduce unneeded costs.

Study on synergistic leaching of potassium and phosphorus from potassium feldspar and solid waste phosphogypsum via coupling reactions

To achieve the resource utilization of solid waste phosphogypsum(PG)and tackle the problem of utilizing potassium feldspar(PF),a coupled synergistic process between PG and PF is proposed in this paper.The study investigates the features of P and F in PG,and explores the decomposition of PF using hydrofluoric acid(HF)in the sulfuric acid system for K leaching and leaching of P and F in PG.The impact factors such as sulfuric acid concentration,reaction temperature,reaction time,material ratio(PG/PF),liquid–solid ratio,PF particle size,and PF calcination temperature on the leaching of P and K is systematically investigated in this paper.The results show that under optimal conditions,the leaching rate of K and P reach more than 93%and 96%,respectively.Kinetics study using shrinking core model(SCM)indicates two significant stages with internal diffusion predominantly controlling the leaching of K.The apparent activation energies of these two stages are 11.92 kJ·mol^(-1)and 11.55 kJ·mol^(-1),respectively.

Selective photosynthesis of Z-olefins through crystalline metal-organic cage-initiated expeditious cascade reactions

The semi-hydrogenation of alkyne to form Z-olefins with high conversion and high selectivity is still a huge challenge in the chemical industry.Moreover,flammable and explosive hydrogen as the common hydrogen source of this reaction increases the cost and danger of industrial production.Herein,we connect the photocatalytic hydrogen evolution reaction and the semihydrogenation reaction of alkynes in series and successfully realize the high selective production of Z-alkenes using low-cost,safe,and green water as the proton source.Before the cascade reaction,a series of isomorphic metal–organic cage catalysts(Co_(x)Zn_(8−x)L_(6),x=0,3,4,5,and 8)are designed and synthesized to improve the yield of the photocatalytic hydrogen production.Among them,Co_(5)Zn_(3)L_(6) shows the highest photocatalytic activity,with a H_(2) generation rate of 8.81 mmol g^(−1) h^(−1).Then,Co_(5)Zn_(3)L_(6) is further applied in the above tandem reaction to efficiently reduce alkynes to Z-alkenes under ambient conditions,which can reach high conversion of>98%and high selectivity of>99%,and maintain original catalytic activity after multiple cycles.This“one-pot”tandem reaction can achieve a highly selective and safe stepwise conversion from water into hydrogen into Z-olefins under mild reaction conditions.

Energetic and Entropic Changes in Volume Work and Chemical Reactions

In the present study, energetic and entropic changes are investigated on a comparative basis, as they occur in the volume changes of an ideal gas in the Carnot cycle and in the course of the chemical reaction in a lead-acid battery. Differences between reversible and irreversible processes have been worked out, in particular between reversibly exchanged entropy (∆eS) and irreversibly produced entropy (∆iS). In the partially irreversible case, ∆eS and ∆iS add up to the sum ∆S for the volume changes of a gas, and only this function has an exact differential. In a chemical reaction, however, ∆eS is independent on reversibility. It arises from the different intramolecular energy contents between products and reactants. Entropy production in a partially irreversible Carnot cycle is brought about through work-free expansions, whereas in the irreversible battery reaction entropy is produced via activated complexes, whereby a certain, variable fraction of the available chemical energy becomes transformed into electrical energy and the remaining fraction dissipated into heat. The irreversible reaction process via activated complexes has been explained phenomenologically. For a sufficiently high power output of coupled reactions, it is essential that the input energy is not completely reversibly transformed, but rather partially dissipated, because this can increase the process velocity and consequently its power output. A reduction of the counter potential is necessary for this purpose. This is not only important for man-made machines, but also for the viability of cells.

Adverse drug reactions of first-line antitubercular drugs:A retrospective study on characteristics,management,factors,and impacts

Objective:To elucidate the characteristics,management strategies,risk factors,and clinical impacts associated with adverse drug reactions(ADRs)induced by first-line antitubercular drugs to enhance tuberculosis(TB)management.Methods:A retrospective cohort study was conducted by retrieving drug-susceptible TB records among adult patients who received TB treatment from 2018 to 2021 at 10 public health clinics in Sarawak,Malaysia.Only the initial TB treatment and occurrence of specific ADRs within the study period were considered.Regression analysis was performed to identify the risk factors associated with both overall ADRs and individual types of ADRs.Results:Among 2953 cases,705(23.9%)developed ADRs.Cutaneous reactions were the most prevalent(47.1%),followed by hepatotoxicity(32.8%)and gastrointestinal disturbances(29.8%).Six out of seven types of ADRs investigated occurred within the intensive phase,mostly manifesting at approximately 2 weeks of initiation.Hepatotoxicity resulted in the majority(85.3%)of treatment discontinuations,while vision problems led to treatment modifications in half of the cases.Risk factors for all ADRs included age≥60 years,females,illicit drug use,and comorbidities such as HIV-positive,diabetes,and chronic liver disease.Alcohol consumption was independently associated with hepatotoxicity.ADRs caused around one-third of interruptions exceeding 2 weeks(33.0%)and subsequently necessitated treatment restarts(34.5%).Conclusions:Understanding these various aspects contributes to improving the overall management of ADRs in TB treatment.Close ADR monitoring and reporting are essential to strengthen ADR management.

Possibility of reaching the predicted center of the“island of stability”via the radioactive beam-induced fusion reactions

Based on the dinuclear system model,the synthesis of the predicted double-magic nuclei^(298)Fl and 304120 was investigated via neutron-rich radioactive beam-induced fusion reactions.The reaction^(58)Ca+^(244)Pu is predicted to be favorable for producing^(298)Fl with a maximal ER cross section of 0.301 pb.Investigations of the entrance channel effect reveal that the^(244)Pu target is more promising for synthesizing^(298)Fl than the neutron-rich targets^(248)Cm and^(249)Bk,because of the influence of the Coulomb barrier.For the synthesis of 304120,the maximal ER cross section of 0.046 fb emerges in the reaction^(58)V+^(249)Bk,indicating the need for further advancements in both experimental facilities and reaction mechanisms.

Decouple charge transfer reactions in the Li-ion battery

In the development of Li-ion batteries(LIBs)with high energy/power density,long cycle-life,fast charging,and high safety,an insight into charge transfer reactions is required.Although electrochemical impedance spectroscopy(EIS)is regarded as a powerful diagnosis tool,it is not a direct but an indirect measurement.With respect to this,some critical questions need to be answered:(i)why EIS can reflect the kinetics of charge transfer reactions;(ii)what the inherent logical relationship between impedance models under different physical scenes is;(iii)how charge transfer reactions compete with each other at multiple scales.This work aims at answering these questions via developing a theory framework so as to mitigate the blindness and uncertainty in unveiling charge transfer reactions in LIBs.To systematically answer the above questions,this article is organized into a three-in-one(review,tutorial,and research)type and the following contributions are made:(i)a brief review is given for impedance model development of the LIBs over the past half century;(ii)an open source code toolbox is developed based on the unified impedance model;(iii)the competive mechanisms of charge transfer reactions are unveiled based on the developed EIS-Toolbox@LIB.This work not only clarifies theoretical fundamentals,but also provides an easy-to-use open source code for EIS-Toolbox@LIB to optimize fast charge/discharge,mitigate cycle aging,and improve energy/power density.

Major challenges and recent advances in characterizing biomass thermochemical reactions

Thermochemical conversions are pathways for biomass utilization to produce various value-added energy and chemical products. For the development of novel thermochemical conversion technologies, an accurate understanding of the reaction performance and kinetics is essential. Given the diversity of the thermal analysis techniques, it is necessary to understand the features and limitations of the reactors, ensuring that the selected thermal analysis reactor meets the specific need for reaction characterization. This paper provides a critical overview of the thermal analysis reactors based on the following perspectives: 1) gas flow conditions in the reactor, 2) particle’s external and internal heat and mass transfer limitations, 3) heating rate, 4) temperature distribution, 5) nascent char production and reaction, 6) liquid feeding and atomization, 7) simultaneous sampling and analyzing of bed materials, and 8) reacting atmosphere change. Finally, prospects and future research directions in the development of analysis techniques are proposed.

One-pot Synthesis of Divalent and Trivalent Cluster Mannosides via Ugi Four-component Reaction

The Ugi four-component reaction (U-4CR) was utilized to prepare divalent and trivalent cluster mannosides. Thus, two target compounds 6 and 8 were obtained efficiently using carboxymethyl 2, 3, 4, 6-tetra-O-acetyl--D-mannopyranoside 4 as acid component, and 1, 6-hexanediamine or tris(2-aminoethyl)amine as the multivalent scaffolds.

Experimental study on reactions between alkaline basaltic melt and orthopyroxenes: constraints on the evolution of lithospheric mantle in the North China Craton

The experimental results of the reactions between an alkaline basaltic melt and mantle orthopyroxenes under high-temperature and high-pressure conditions of 1300–1400℃ and 2.0–3.0 GPa using a six-anvil apparatus are reported in this paper.The reactions are proposed to simulate the interactions between melts from the asthenospheric mantle and the lithospheric mantle.The starting melt in the experiments was made from the alkaline basalt occurring in Fuxin,Liaoning Province,and the orthopyroxenes were separated from the mantle xenoliths in Damaping,Hebei Province.The results show that clinopyroxenes were formed in all the reactions between the alkaline basaltic melt and orthopyroxenes under the studied P–T conditions.The formation of clinopyroxene in the reaction zone is mainly controlled by dissolution–crystallization,and the chemical compositions of the reacted melt are primarily infl uenced by the diff usion eff ect.Temperature is the most important parameter controlling the reactions between the melt and orthopyroxenes,which has a direct impact on the melting of orthopyroxenes and the diff usion of chemical components in the melt.Temperature also directly controls the chemical compositions of the newly formed clinopyroxenes in the reaction zone and the reacted melt.The formation of clinopyroxenes from the reactions between the alkaline basaltic melt and orthopyroxenes can result in an increase of CaO and Al_(2)O_(3) contents in the rocks containing this mineral.Therefore,the reactions between the alkaline basaltic melt from the asthenospheric mantle and orthopyroxenes from the lithospheric mantle can lead to the evolution of lithospheric mantle in the North China Craton from refractory to fertile with relatively high CaO and Al 2 O 3 contents.In addition,the reacted melts in some runs were transformed from the starting alkaline basaltic into tholeiitic after reactions,indicating that tholeiitic magma could be generated from alkaline basaltic one via reactions between the latter and orthopyroxene.

Highly mass activity electrocatalysts with ultralow Pt loading on carbon black for hydrogen evolution reaction

Pt-based nanocatalysts offer excellent prospects for various industries.However,the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge.In this study,nanocatalysts with ultralow Pt content,excellent performance,and carbon black as support were prepared through in-situ synthesis.These~2-nm particles uniformly and stably dispersed on carbon black because of the strong s-p-d orbital hybridizations between carbon black and Pt,which suppressed the agglomeration of Pt ions.This unique structure is beneficial for the hydrogen evolution reaction.The catalysts exhibited remarkable catalytic activity for hydrogen evolution reaction,exhibiting a potential of 100 mV at 100 mA·cm^(-2),which is comparable to those of commercial Pt/C catalysts.Mass activity(1.61 A/mg)was four times that of a commercial Pt/C catalyst(0.37 A/mg).The ultralow Pt loading(6.84wt%)paves the way for the development of next-generation electrocatalysts.

Boosting Oxygen Evolution Reaction Performance on NiFe‑Based Catalysts Through d‑Orbital Hybridization

Anion-exchange membrane water electrolyzers(AEMWEs)for green hydrogen production have received intensive attention due to their feasibility of using earth-abundant NiFe-based catalysts.By introducing a third metal into NiFe-based catalysts to construct asymmetrical M-NiFe units,the d-orbital and electronic structures can be adjusted,which is an important strategy to achieve sufficient oxygen evolution reaction(OER)performance in AEMWEs.Herein,the ternary NiFeM(M:La,Mo)catalysts featured with distinct M-NiFe units and varying d-orbitals are reported in this work.Experimental and theoretical calculation results reveal that the doping of La leads to optimized hybridization between d orbital in NiFeM and 2p in oxygen,resulting in enhanced adsorption strength of oxygen intermediates,and reduced rate-determining step energy barrier,which is responsible for the enhanced OER performance.More critically,the obtained NiFeLa catalyst only requires 1.58 V to reach 1 A cm^(−2) in an anion exchange membrane electrolyzer and demonstrates excellent long-term stability of up to 600 h.