Copper(II) Perfluorinated Carboxylate Complexes with Small Aliphatic Amines as Universal Precursors for Nanomaterial Fabrication

Copper(II) carboxylate compounds with ethylamine and isopropylamine of the general formula [Cu2(RNH2)2(µ-O2CRf)4], where R = Et, iPr, and Rf = CnF2n+1, n = 1–6, were characterised in the condensed and gas phases by electron impact mass spectrometry (EI MS), IR spectroscopy, and thermal analysis. A mass spectra analysis confirmed the presence of metallated species in the gas phase. Among the observed fragments, the pseudomolecular ions [Cu2(RNH2)2(µ-O2CRf)3]+ were found, which suggests the dimeric structure of the studied complexes with axially N-coordinated ethyl- or isopropylamine molecules and bridging perfluorinated carboxylates. TGA studies demonstrated that copper transfer to the gas phase occurs even under atmospheric pressure. The temperature range of the [Cu2(RNH2)2(µ-O2CRf)4] and other copper carriers detection, observed in variable temperature infrared spectra, depends on the type of amine. The possible mechanisms of the decomposition of the tested compounds are proposed. The copper films were produced without additional reducing agents despite using Cu(II) CVD precursors in the chemical vapor deposition experiments. The layers of the gel-like complexes were fabricated in both spin- and dip-coating experiments, resulting in copper or copper oxide materials when heated. Dinuclear copper(II) carboxylate complexes with ethyl- and isopropylamine [Cu2(RNH2)2(µ-O2CRf)4] can be applied for the formation of metal or metal oxide materials, also in the nanoscale, by vapour and ‘wet’ deposition methods.

Substituent Effects on EI-MS Fragmentation Patterns of 5-Allyloxy-1-aryl-tetrazoles and 4-Allyl-1-aryl-tetrazole-5-ones; Correlation with UV-Induced Fragmentation Channels

1,4- and 1,5-disubstituted tetrazoles possess enriched structures and versatile chemistry, representing a challenge for chemists. In the present work, we unravel the fragmentation patterns of a chemically diverse range of 5-allyloxy-1-aryl-tetrazoles and 4-allyl-1-aryl-tetrazolole-5-ones when subjected to electron impact mass spectrometry (EI-MS) and investigate the correlation with the UV-induced fragmentation channels of the matrix-isolated tetrazole derivatives. Our results indicate that the fragmentation pathways of the selected tetrazoles in EI-MS are highly influenced by the electronic effects induced by substitution. Multiple pathways can be envisaged to explain the mechanisms of fragmentation, frequently awarding common final species, namely arylisocyanate, arylazide, arylnitrene, isocyanic acid and hydrogen azide radical cations, as well as allyl/aryl cations. The identified fragments are consistent with those found in previous investigations concerning the photochemical stability of the same class of molecules. This parallelism showcases a similarity in the behaviour of tetrazoles under EI-MS and UV-irradiation in the inert environment of cryogenic matrices of noble gases, providing efficient tools for reactivity predictions, whether for analytical ends or more in-depth studies. Theoretical calculations provide complementary information to articulate predictions of resulting products.

Submersion of rubidium clusters in helium nanodroplets

Alkali atoms and small clusters are known to reside on the surface of a helium droplet rather than its inside as most other dopant species. A theoretical investigation suggested that alkali clusters (Li–Rb) exceeding a certain critical size can become submerged in the droplet, which was experimentally confirmed for sodium and potassium. Here, we report an analogous experimental study of rubidium cluster submersion by means of electron impact mass spectrometry. We recorded size distributions of Rb cluster ions at various electron energies between 8 and 160 eV. Our data suggest that Rb clusters attached to helium droplets undergo a gradual submersion transition similar to potassium, ultimately leading to the full submersion of clusters larger than $$\sim 100~\hbox {Rb}$$ ∼ 100 Rb atoms. Our findings are consistent with previous theoretical and experimental studies. Graphic abstract

Synthesis, Characterization and Thermal Study of Divalent Germanium, Tin and Lead Triazenides for Atomic Layer Deposition

<p>The number of M–N bonded divalent group 14 precursors suitable for atomic layer deposition is limited, in particular for Ge and Pb. A majority of the reported precursors are dicoordinated, with the only tetracoordinated example being the Sn(II) amidinate. No such Ge(II) and Pb(II) compounds have been demonstrated. Herein, we present tetracoordinated Ge(II), Sn(II) and Pb(II) complexes bearing two sets of the bidentate 1,3-di-<i>tert</i>-butyl triazenide ligands. These compounds are highly volatile and show ideal behavior by thermogravimetric analysis. However, they have unusual thermal properties and exhibit instability during sublimation. Interestingly, the instability is not only temperature dependent but also facilitated by reduced pressure. Using quantum-chemical density functional theory, a gas-phase decomposition pathway was mapped out. The pathway account for the unusual thermal behavior of the compounds and is supported by electron impact mass spectrometry data.</p>

Synthesis, Characterization and Thermal Study of Divalent Germanium, Tin and Lead Triazenides for Atomic Layer Deposition

<p>The number of M–N bonded divalent group 14 precursors suitable for atomic layer deposition is limited, in particular for Ge and Pb. A majority of the reported precursors are dicoordinated, with the only tetracoordinated example being the Sn(II) amidinate. No such Ge(II) and Pb(II) compounds have been demonstrated. Herein, we present tetracoordinated Ge(II), Sn(II) and Pb(II) complexes bearing two sets of the bidentate 1,3-di-<i>tert</i>-butyl triazenide ligands. These compounds are highly volatile and show ideal behavior by thermogravimetric analysis. However, they have unusual thermal properties and exhibit instability during sublimation. Interestingly, the instability is not only temperature dependent but also facilitated by reduced pressure. Using quantum-chemical density functional theory, a gas-phase decomposition pathway was mapped out. The pathway account for the unusual thermal behavior of the compounds and is supported by electron impact mass spectrometry data.</p>

Determination of Phosphodiesterase Type 5 Enzyme (PDE-5) Inhibitors and Analogues as Adulterants in Selected Herbal Products using Gas Chromatography–Electron Impact-Mass Spectrometer (GC-EI-MS)

Sildenafil, tadalafil, and vardenafil are phosphodiesterase type 5 enzyme (PDE-5) inhibitors used for the treatment of male erectile dysfunction. This present study aims to investigate 55 herbal products indicated for men’s sexual health from the Malaysian market for adulteration of PDE-5 inhibitors and analogues. The screening and identification of 20 PDE-5 inhibitors and analogues in herbal products of various forms (powder, capsules, tablets, and pastels) were conducted using gas chromatography–electron impact-mass spectrometer (GC-EI-MS). The analysis has shown that 19 herbal products were adulterated with PDE-5 inhibitors and analogues. Unique ion fragmentations and the presence of molecular ion serve as potential markers, and the limit of detection (LOD) was 0.1-5.0 µg/g. Ten PDE-5 inhibitors and analogues were randomly selected and successfully validated for simultaneous quantification, whereby the limit of quantitation (LOQ) was 5.0–50.0 µg/g with recoveries at 86.1-118.9%. The developed method of GC-EI-MS was shown to be simple, throughput, economical and had sufficient sensitivity to screen, identify and quantify PDE-5 inhibitors and analogues in herbal matrices.

On the mass spectrometric fragmentations of the bacterial sesterterpenes sestermobaraenes A–C

A 13C-labelling was introduced into each individual carbon of the recently discovered sestermobaraenes by the enzymatic conversion of the correspondingly 13C-labelled isoprenyl diphosphate precursors with the sestermobaraene synthase from Streptomyces mobaraensis. The main compounds sestermobaraenes A, B, and C were analysed by gas chromatography–mass spectrometry (GC–MS), allowing for a deep mechanistic investigation of the electron impact mass spectrometry (EIMS) fragmentation reactions of these sesterterpene hydrocarbons.

Mammalian exocrine secretions XIX. Chemical characterization of the interdigital secretion of the Black Wildebeest, Connochaetes gnou

Using gas chromatography (GC) in conjunction with electron impact mass spectrometry and retention-time comparison, 94 compounds, ranging from 2-methyl-2-propenal to octadecanoic acid, were identified in the interdigital secretions of male and female black wildebeests, Connochaetes gnou (also known as the white-tailed gnu). The constituents of these secretions belong to many different compound classes, including hydrocarbons, alcohols, aromatics and aliphatic carbonyl compounds including carboxylic acids as well as carboxylic acid esters. Relatively small quantitative differences were found between the male and female interdigital secretions. It was concluded that these compounds probably do not play a significant role in territorial marking or in chemical communication between males and females of the species, but they could be involved in preserving the remarkably strong attachment between members of social subgroups in black wildebeest populations.

Effects of nanoemulsion and essential oil from the leaves of Ocotea elegans against Dysdercus peruvianus

The Dysdercus peruvianus Guérin-Méneville is commonly known as the cotton stainer bug. In this study, it was evaluated the insecticide activity and mode of action of the essential oil from leaves of Ocotea elegans Mez and its nanoemulsion against D. peruvianus. Leaves of O. elegans were extracted by hydrodistillation. The essential oil obtained was analyzed by gas chromatography coupled with electron impact mass spectrometry and flame ionization detector. The essential oil toxicity measured by lethal dose 50 (LD50) and survival rate of insects were recorded. Lastly, an assay was carried out to assess the inhibition of the enzyme acetylcholinesterase to determine a possible mechanism of action of insecticidal activity. The sesquiterpene sesquirosefuran was the major compound detected and corresponds to 92% of the components of the essential oil. The nanoemulsion more stable showed hydrophilic lipophilic balance (HLB 11.74), droplet size 92±1.80 nm, and polydispersity index (PDI of 0.215±0.015). After the topical application of the O. elegans essential oil, significant decreases in the survival of D. peruvianus occurred in a dose-response manner with LD50 = 162.18 μg and the survival rate of the nanoemulsion in D. peruvianus was 10.0±5.47, a better value than in pure essential oil. The acetylcholinesterase inhibition presented inhibition concentration (IC50 = 1.37mg/mL) and mixed type of inhibition. This indicates that the essential oil of leaves from O. elegans and its nanoemulsion are promising candidates for use in integrated pest management programs.