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John Wiley & Sons, Inc.
Chemistry Select

John Wiley & Sons, Inc.

Chemistry Select/Journal Chemistry Select
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    A DFT Study on the Mechanism of Active Species in Selective Photocatalytic Oxidation of Toluene into Benzaldehyde on(WO3)3 Clusters

    Bin WangYu-Feng DingShuang-Feng Yin
    10页
    查看更多>>摘要：It is of great significance to transform toluene into value-added aldehydes under mild conditions,but the oxidation mechanism is still unclear,which seriously hinders the development of this direction.To reveal the nature of photocatalytic reaction,we studied the reaction mechanism of photocatalytic selective oxidation of toluene into benzaldehyde(BAD)on(WO3)3 clusters by density functional theory calculation,and analyzed the effect of active species on the reaction,including electrons,holes,dissolved oxygen(O2),superoxide radical anions(*O2),hydroxyl radicals(*OH)and hydroperoxyl radicals(*OOH).The results show that *OH and *OOH play a major role in the reaction,from which we summarized two main pathways for BAD production.The direct oxidation of toluene to BAD is dominated by *OOH and has higher selectivity.The oxidation process dominated by *OH first converts toluene to benzyl alcohol(BA),and then BA continues to be oxidized to BAD.This path is more thermally advantageous because the dehydration energy barrier of C6H5CHOHOH(IM5)(22.3 kcalmol1)is lower than that of C6H5CH2OOH(IM2)(42.9 kcalmol 1).However,the selectivity of this path is low because *OH and holes can easily oxidize BAD to benzoic acid.Notably,water molecules reduced the energy barrier for dehydration of IM2 and IM5 by 12.4 kcalmol1 and 13.0 kcalmol1,respectively.The results elucidate the mechanism of free radicals involved in the photocatalytic reaction at molecular level.
      原文链接:
    • NSTL

    Visible-Light Enabled Late-Stage,Room-Temperature Aminocarbonylation of Aryl Iodides with Labeled Carbon Monoxide

    Kim S.MuhlfenzlMalvika SardanaTroels Skrydstrup
    6页
    查看更多>>摘要：In recent years,coupling reactions mediated by visible light have been widely studied because such reactions can often be run at significantly lower temperatures.In this work,aryl iodides were coupled with amines at ambient temperature in the presence of stoichiometric amounts of carbon monoxide using visible-light irradiation and palladium catalysis.A wide range of aryl substrates,both electron-deficient and rich,as well as heterocycles,were carbonylated to provide the corresponding amides in moderate to good yields based on CO.In addition,the generality of the amine was investigated,and primary and secondary amines yielded the desired products in moderate to good yields.This methodology was also successfully applied to the synthesis of pharmaceuticals and the incorporation of a carbon-14 label into the carbonyl group,where the use of 9-methyl-fluorene-9-carbonyl chloride(COgen)as the carbon isotope-labeled CO source allowed easy translation between the unlabeled and the labeled transformations.
      原文链接:
    • NSTL

    Structural,Spectroscopic Characterization and Application of a Co(II)Coordination Polymer[Co(suc)(bpm)]·2H2O

    Luann R.D’souzaNikita N.HarmalkarSunder N.Dhuri
    11页
    查看更多>>摘要：A Co(II)coordination polymer[Co(suc)(bpm)]·2H2O(1)built from succinate(suc)and bipyrimidine(bpm)is synthesized hydrothermally and characterized by different methods.It crystallizes in a monoclinic space group P21/n with an intriguing 3D polymeric architecture.The weak antiferromag-netic(AF)exchange interactions were evinced by Curie Constant(C)= 1.803 cm~3mol~(-1)K and a negative Weiss constant(φ)= 30.163 K.Type VI adsorption isotherm behavior of 1 at 77 K revealed its non-porous property.Compound 1 was investigated and successfully utilized as an additive in lowering the decomposition temperature of ammonium nitrate(AN)based fuels as demonstrated from TG and DSC experiments performed in nitrogen atmosphere.
      原文链接:
    • NSTL

    Contrasting the Noncovalent Interactions of Aromatic Sulfonyl Fluoride and Sulfonyl Chloride Motifs via Crystallography and Hirshfeld Surfaces

    Sophia BelliaLara I.TeodoroAntonio J.Barbosa
    9页
    查看更多>>摘要：A heteroaryl sulfonyl(VI)fluoride,4-chloro-7-fluorosulfonyl-2,1,3-benzoxadiazole,was synthesized from its chloride counterpart(4-chloro-7-chlorosulfonyl-2,1,3-benzoxadiazole)and the X-ray structure analysis of these compounds and the interactions in the solid-state were thoroughly examined.Hirshfeld surface analysis is used to provide a thorough and complete picture of the changes arising from the different halides in the functional groups.Surface analysis reveals that the fluoride does not participate in any hydrogen interactions as opposed to the chloride.However,the fluorine atom is observed to form close interactions with several π bonds.For both moieties,however,the sulfonyl oxygens show comparable interactions with respect to both magnitude and interatomic distances.The Hirshfeld surface analysis is coupled with computational studies to help elucidate the observed interactions that are found from the distinct nitrogen,chlorine,and oxygen atoms present in the molecules,providing new physical insights to the correlation between their structures and properties
      原文链接:
    • NSTL

    Microwave-Assisted Tandem Copper-Catalyzed Three-Component Reaction for Synthesis of 2-Iminopyrans

    Sivakumar ShanmugamKamaraj PasumponVaithiyanathan Mahendran
    5页
    查看更多>>摘要：The iminopyrans were synthesized by the CuAAC-MCR approach,the coupling of enaminones,phenyl acetylenes,and sulfonyl,under microwave treatment.The mechanism of the formation of iminopyrans along with amidine has been studied in detail.Experiments to minimize amidine formation were explored,and unfortunately,these experiments were unsuc-cessful.Molar equivalents of enaminones,phenyl acetylenes,and sulfonyl were optimized to increase the yield of iminopyr-an.Fluorescent properties of iminopyrans were characterized using Frontier molecular orbital analysis,UV absorption,and emission studies.
      原文链接:
    • NSTL

    Two-and Three-Phase Self-assembly of Molecular Capsules

    Alexander ShivanyukOleksandra LagernaGrygoriy A.Dolgonos
    8页
    查看更多>>摘要：Two-and three-phase molecular encapsulations of Me4N~+or C7H_7~+in the hydrogen-bonded dimers of resorcin[4]arene tetraphosphates enable ion pair separations,dissolution of solid capsule components,and stabilization of capsule-separated ion pairs in solution.Self-assembly of the capsular ion pairs,the exchange of the encapsulated cations and external anions as well as the formation of heterodimeric capsular complexes are slow on hours time scale in heterogeneous systems and instantaneous in solutions.Spectroscopic studies and molecular modeling related the properties of the capsule-separated ion pairs to the energies of induced conformational changes,hydrogen bonding,host-guest interactions,ion pair separation,and the relative polarity of the solvent.
      原文链接:
    • NSTL

    Bismuth Oxychloride Nanoparticles:Deep Eutectic Solvent Assisted Synthesis and Application in an Electrochemical Nickel Sensor

    Neda RahmatiMostafa RahimnejadS.Masoomeh Pourali
    10页
    查看更多>>摘要：A safe,green,and cost-effective procedure is introduced for synthesizing bismuth oxychloride(BiOCl)nanoparticles as an alternative to the time-consuming ones with hazardous chemicals.In this regard,BiOCl was synthesized in both nanoplates and nanoflowers morphologies employing choline chloride:a urea-based deep eutectic solvent,as a green solvent through the popular solvothermal and anion exchange synthesis approach.Accordingly,nano-flowers and nano-plates of BiOCl were synthesized by exposing {010} and {001} facets,respectively,while different characterization techniques showed excellent patterns and high purity of the synthesized nanoparticles.They are exploited as electrode modifiers for fabricating a high-performance electrochemical nickel ion sensor to control the quality of water,and industrial waste liquor concentrates.The adsorption stripping voltammetry technique revealed that the electrode used for nickel detection with BiOCl nano-plates was more sensitive than with BiOCl nano-flowers.To achieve optimal electrochemical values for the proposed sensor,variables interactions are investigated using the central composite design method.The limit of detection,the electron transfer coefficient,and the number of transferred electrons were obtained to be 0.26 μm,0.166,and 1,respectively.Evaluating the sensor application in the presence of other heavy metal cations showed its promising capability of nickel ion detection in real samples.
      原文链接:
    • NSTL

    Synthesis and Characterizations of Core-Shell Hybrids of Poly(ortho-phenylenediamine)Functionalized with Uniformly Distributed Silver Nanoparticles

    Moon ChourasiaDevleena SahooLeena Priya
    8页
    查看更多>>摘要：A single-step process has been demonstrated for the synthesis of core-shell hybrid of poly(o-phenylenediamine)functionalized with uniformly distributed silver nanoparticles.The silver nano-particles as core were formed by the thermal reduction of the amine complexes of silver mono-positive cation.The interfacial functionalization of silver nanoparticles by the =NH was characterized using Fourier transform infrared spectroscopy and ultraviolet-visible spectroscopy.The uniform size of particles in core-shell hybrid and the amount of metal nano-particle ingrained in polymer matrix were confirmed from the characterizations,viz.,dynamic light scattering,inductively coupled plasma-optical emission spectrometry and field-emission scanning electron microscopy.The hybrid with ~12% silver loading was found to have the highest DC-conductivity of 104Scm1 range,even without the usage of any other dopant.The induced doping of silver nanoparticles through the functional groups of the polymer was considered to explain the conducting properties of the prepared core-shell hybrid.
      原文链接:
    • NSTL

    A Series of Adenosine Analogs as the First Efficacious Anti-SARS-CoV-2 Drugs against the B.1.1.529.4 Lineage:A Preclinical Repurposing Research Study

    Amgad M.RabieMohnad Abdalla
    17页
    查看更多>>摘要：Given the rapid progression of the coronavirus disease 2019(COVID-19)pandemic,an ultrafast response was urgently required to handle this major public crisis.To contain the pandemic,investments are required to develop diagnostic tests,prophylactic vaccines,and novel therapies.Lately,nucleoside analog(NA)antivirals topped the scene as top options for the treatment of COVID-19 caused by the severe acute respiratory syndrome coronavirus 2(SARS-CoV-2)infections.Meanwhile,the continuous generation of new lineages of the SARS-CoV-2 Omicron variant caused a new challenge in the persistent COVID-19 battle.Hitting the two crucial SARS-CoV-2 enzymes RNA-dependent RNA polymerase(RdRp)and 3’-to-5'exoribonuclease(ExoN)collectively together using only one single ligand is a very successful new approach to stop SARS-CoV-2 multiplication and combat COVID-19 irrespective of the SARS-CoV-2 variant type because RdRps and ExoNs are broadly conserved among all SARS-CoV-2 strains.Herein,the current comprehensive study investigated most NAs libraries,searching for the most ideal drug candidates expectedly able to perfectly act through this double tactic.Gradual computational filtration gave rise to six different promising NAs,which are riboprine,forodesine,tecadenoson,nelarabine,vidarabine,and maribavir,respectively.Further biological assessment proved for the first time,using the in vitro anti-RdRp/ExoN and anti-SARS-CoV-2 bioassays,that riboprine and forodesine,among all the six tested NAs,are able to powerfully inhibit the replication of the new virulent strains of SARS-CoV-2 with extremely minute in vitro anti-RdRp and anti-SARS-CoV-2 EC50 values of about 0.22 and 0.49 μM for riboprine and about 0.25 and 0.73 μM for forodesine,respectively,surpassing both remdesivir and the new anti-COVID-19 drug molnupiravir.The prior in silico data supported these biochemical findings,suggesting that riboprine and forodesine molecules strongly hit the key catalytic pockets of the SARS-CoV-2(Omicron variant)RdRp’s and ExoN’s main active sites.Additionally,the ideal pharmacophoric features of riboprine and forodesine molecules render them typical dual-action inhibitors of SARS-CoV-2 replication and proofreading,with their relatively flexible structures open for diverse types of chemical derivatization.In Brief,the current important results of this comprehensive study revealed the interesting repurposing potentials of,mainly,the two nucleosides riboprine and forodesine to effectively shut down the polymerase/exoribonuclease-RNA nucleotides interactions of the SARS-CoV-2 Omicron variant and consequently treat COVID-19 infections,motivating us to rapidly begin the two drugs'broad preclinical/clinical anti-COVID-19 bioevaluations,hoping to combine both drugs soon in the COVID-19 treatment protocols.
      原文链接:
    • NSTL

    Rapid and Visual Detection of Al~(3+)Based on Supramolecular Self-Assembly of a Water-Soluble Perylene Diimide Derivative

    Mei ShiJinghan JiangXiao Gao
    4页
    查看更多>>摘要：Aluminum(Al)is widely used in food industry,but excessive absorption of Al~(3+)causes many serious health problems.Therefore,it is of great significance to determine the specificity of Al~(3+).In this study,we designed and synthesized a water-soluble perylene diimide derivative(PDI-Phe)for monitoring Al~(3+)rapidly and visually.Through absorption and emission spectroscopy techniques,we systematically explored the properties and mechanism of the sensor to Al~(3+).The limit of detection(LOD)of Al~(3+)was as low as 6.54 nM.And with the existence of Al~(3+),electrostatic interaction and intermolecular π-π stacking promoted the aggregation and fluorescence quenching of PDI-Phe.Even in the presence of other analytes,PDI-Phe still had excellent selectivity and sensitivity for Al~(3+)detection.Besides,it also had the characteristics of low cost,good water solubility,excellent chemical and optical stability,and easy synthesis.Finally,this method can be further applied to tap water samples.
      原文链接:
    • NSTL