Electrospun Nanofibers from a Tricyanofuran‐Based Molecular Switch for Colorimetric Recognition of Ammonia Gas

A chromophore based on tricyanofuran (TCF) with a hydrazone (H) recognition moiety was developed. Its molecular‐switching performance is reversible and has differential sensitivity towards aqueous ammonia at comparable concentrations. Nanofibers were fabricated from the TCF–H chromophore by electrospinning. The film fabricated from these nanofibers functions as a solid‐state optical chemosensor for probing ammonia vapor. Recognition of ammonia vapor occurs by proton transfer from the hydrazone fragment of the chromophore to the ammonia nitrogen atom and is facilitated by the strongly electron withdrawing TCF fragment. The TCF–H chromophore was added to a solution of poly(acrylic acid), which was electrospun to obtain a nanofibrous sensor device. The morphology of the nanofibrous sensor was determined by SEM, which showed that nanofibers with a diameter range of 200–450 nm formed a nonwoven mat. The resultant nanofibrous sensor showed very good sensitivity in ammonia‐vapor detection. Furthermore, very good reversibility and short response time were also observed.     

Ammonia Oxidation Enhanced by Photopotential Generated by Plasmonic Excitation of a Bimetallic Electrocatalyst

We study how visible light influences the activity of an electrocatalyst composed of Au and Pt nanoparticles. The bimetallic composition imparts a dual functionality: the Pt component catalyzes the electrochemical oxidation of ammonia to liberate hydrogen and the Au component absorbs visible light by the excitation of localized surface plasmon resonances. Under visible-light excitation, this catalyst exhibits enhanced electrochemical ammonia oxidation kinetics, outperforming previously reported electrochemical schemes. We trace the enhancement to a photochemical potential resulting from electron–hole carriers generated in the electrocatalyst by plasmonic excitation. The photopotential responsible for enhanced kinetics scales linearly with the light intensity—a general design principle for eliciting superlative photoelectrochemical performance from catalysts comprised of plasmonic metals or hybrids. We also determine a photochemical conversion coefficient.     

A Photoluminescent Ag10Cu6 Cluster Stablized by a PNNP Ligand and Phenylacetylides Selectively and Reversibly Senses Ammonia in Air and Water

A photoluminescent bimetallic cluster [Ag₁₀Cu₆(bdppthi)₂(C≡CPh)₁₂(MeOH)₂(H₂O)](ClO₄)₄ ( 1 , bdppthi=N,N’-bis(diphenylphosphanylmethyl)-tetrahydroimidazole} was synthesized from the PNNP type ligand bdppthi generated in-situ. Upon excitation at 365 nm, 1 exhibited strong phosphorescent emission at 630 nm, which was selectively quenched by NH₃ in air or water. The sensing of NH₃ was rapid and recoverable, with detection limits of 53 ppm (v/v) in N₂ and 21 μmol/L (0.36 ppm, w/w) for NH₃ ⋅ H₂O in water. Cluster 1 could potentially serve as a bifunctional chemical sensor for the efficient detection of ammonia in waste-gas and waste-water.     

Formation of an Azaruthenacyclopentadiene Skeleton via Ammonia Activation by an Electron-Deficient Ru3 Cluster

A dicationic triruthenium complex containing a μ₃-η³-C₃ ring, [(Cp*Ru)₃(μ₃-η³-C₃MeH₂−)(μ₃-CH)(μ-H)]²⁺ ( 1 a , Cp*=η⁵-C₅Me₅), reacted with ammonia to yield a μ-amido complex, [(Cp*Ru)₃(μ₃-η³-CHCMeCH) (μ₃-CH)(μ-NH₂)]²⁺ ( 5 ), via N−H bond scission. Subsequent treatment with base resulted in C−N bond formation to yield a μ₃-η²:η²-1-azabutadien-4-yl complex, [(Cp*Ru)₃(μ₃-CH)(μ₃-η²:η²-NH=CH−CMe=CH−)]⁺ ( 6 a ). The azaruthenacyclopentadiene skeleton was alternatively synthesized by the photolysis of mono-cationic complex [(Cp*Ru)₃(μ₃-η³-C₃RH₂−)(μ₃-CH)]⁺ ( 2 a ; R=Me, 2 b ; R=H) in the presence of ammonia. The C₃ ring skeleton was broken via the electron transfer to the π*(C−C) orbital in the C₃ ring, and a transiently generated unsaturated μ₃-allylic species can take up ammonia, resulting in N−H bond scission followed by C−N bond formation.     

Selective Probing of Gaseous Ammonia Using Red‐Emitting Carbon Dots Based on an Interfacial Response Mechanism

Solid‐state fluorescence sensing is one of the most appealing detection techniques because of its simplicity and convenience in practical operation. Herein, we report the development of a red‐emitting carbon dots (RCDs)‐based material as a solid‐state fluorescence sensor for the selective probing of gaseous ammonia. The RCDs were prepared by a low‐cost, one‐step carbonization method using sugar cane bagasse as the carbon precursor. The pristine RCDs were then directly coated on polyvinylidene fluoride membrane to produce a new fluorescence sensor capable of selectively distinguishing toxic gaseous ammonia from other analyte vapors through sensitive fluorescence quenching with a low detection limit. More importantly, the interfacial response mechanism occurring on the surface of the RCDs has been studied by X‐ray photoelectron spectroscopy, Fourier‐transform infrared spectroscopy, and Raman measurements. The results indicate that fluorescence quenching in the RCDs might result from ammonia‐induced Michael addition through insertion of N into the C?C group and deprotonation of the carboxyl group. To the best of our knowledge, this is the first report that provides clear insight into the mechanism of surface chemistry on CDs in the solid state.     

Nickel‐Catalyzed Amination of Aryl Chlorides with Ammonia or Ammonium Salts

The nickel‐catalyzed amination of aryl chlorides to form primary arylamines occurs with ammonia or ammonium sulfate and a well‐defined single‐component nickel(0) precatalyst containing a Josiphos ligand and an η²‐bound benzonitrile ligand. This system also catalyzes the coupling of aryl chlorides with gaseous amines in the form of their hydrochloride salts.     

Ammonia Activation by a Nickel NCN‐Pincer Complex featuring a Non‐Innocent N‐Heterocyclic Carbene: Ammine and Amido Complexes in Equilibrium

A Ni⁰‐NCN pincer complex featuring a six‐membered N‐heterocyclic carbene (NHC) central platform and amidine pendant arms was synthesized by deprotonation of its Ni^II precursor. It retained chloride in the square‐planar coordination sphere of nickel and was expected to be highly susceptible to oxidative addition reactions. The Ni⁰ complex rapidly activated ammonia at room temperature, in a ligand‐assisted process where the carbene carbon atom played the unprecedented role of proton acceptor. For the first time, the coordinated (ammine) and activated (amido) species were observed together in solution, in a solvent‐dependent equilibrium. A structural analysis of the Ni complexes provided insight into the highly unusual, non‐innocent behavior of the NHC ligand.     

Reactions of Polyarsenides with Acetylene: Synthesis and Characterization of [Cs([18]crown‐6)]2As7C14H11·6NH3 and As2C6H6

The reaction of Cs₃As₇ with diphenylacetylene in the presence of 18 crown‐6 in liquid ammonia results in the formation of the new compound [Cs( 18 crown‐6)]₂As₇C₁₄H₁₁ · 6NH₃, which crystallizes in black monoclinic crystals. It contains the first monosubstituated heptaarsenide anion with a hydrocarbon‐only substituent and theoretical calculations show a significant influence of the organic substituent on the electronic structure within the cage. The (Z)‐1, 2‐diphenylethenyl‐heptaarsenide di‐anion can be seen as the first step towards the formation of 1, 2,3‐triarsolides. Further experiments regarding the reaction of Rb₃As₁₁ and Cs₃As₁₁ with acetylene gas in liquid ammonia reveal the formation of the diarsabarrelene As₂C₆H₆, which crystallizes as colorless orthorhombic crystals. Calculations based on the structural data obtained by X‐ray crystallography show the electronically inert character of the arsenic lone pair.     

纳氏试剂分光光度法测定铝灰渣浸出液中的氨氮含量

随着水土资源环境日益恶化,监测氨氮量对水土的污染程度也备受关注。为了准确测定铝灰渣浸出液中的氨氮量,实验对振荡方法、振荡时间、固液比、试液过滤方式、纳氏试剂加入量以及测定干扰因素进行了研究。确定了以翻转振荡为前处理方式,最佳振荡时间为14 h,固液比为1:10,最佳纳氏试剂加入量为1.0 mL,通过改善过滤方式,降低了空白值。由实验结果可知：在试验范围内,F^-对氨氮量的测定不产生干扰;对于浸出液中Cl^-、Al³⁺和Ca²⁺浓度高的样品,可通过移取稀释液2.00 mL,加入1.0 mL酒石酸钾钠溶液(500 g/L),即可消除其干扰。运用纳氏试剂分光光度法测定铝灰渣浸出液中的氨氮量,得到氨氮标准曲线线性相关系数为0.9998,方法检出限为0.39 mg.L^-1,RSD(n=6)<5%,回收率在94.7%～105%之间。本方法简单快速,精密度高,且具有较低的检出限,适用于大批量铝灰铝渣等固体废物浸出液中氨氮量的测定。     

Preparation of quaternarized N-halamine-grafted graphene oxide nanocomposites and synergetic antibacterial properties

At present, frequent outbreaks of bacteria and viruses have seriously affected people's normal lives. Therefore, the study of broad-spectrum antibacterial nanocomposites is very promising. However, most antibacterial materials have some disadvantages, such as single bactericidal mechanisms and unrepeatable use. Based on the current situation, a kind of nanocomposite with three structures of graphene oxide (GO), quaternary ammonium salt (QAs) and N-halamine was prepared, which showed synergistic effect to improve antibacterial activity and combined with a variety of sterilization mechanisms. Meanwhile, GO can provide richer ways of sterilization and high specific surface area, which is conducive to the grafting of quaternarized N-halamine. The advantages of physical sterilization of GO, charge adsorption of QAs, reuse of N-halamine and efficient sterilization are fully utilized. The results showed that the quaternarized N-halamine-grafted GO was obtained successfully. GO grafted with quaternarized N-halamine polymer showed strong speedy bactericidal activity against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) (99%). It had good storage and regeneration properties.