Search Results (33)

In order to investigate the coordination chemistry of O-alkyl N-aryl thiocarbamate ligands, HgI₂ was reacted with one equivalent of PrOC(=S)N(H)Ph L in toluene solution to afford the 1D polymeric title compound [{IHg(μ-I)}{κ¹-PrOC(=S)N(H)Ph}]_n CP1. The formation of this iodide-bridged coordination polymer was ascertained by a single-crystal X-ray diffraction study performed at 100 K, as well as the formation of an adduct between anilinium chloride and L forming a supramolecular ribbon of composition [L(PhNH₃)(Cl)]. The occurrence of anilinium chloride is due to the partial hydrolysis of L in the presence of HCl. Full article

The aim of this study is to prepare new cellulose derivatives that show good feasibility and processability. Accordingly, in this study, we demonstrate Michael addition to hydroxyalkyl acrylates, that is, 2-hydroxyethyl and 4-hydroxybutyl acrylates (HEA and HBA, respectively), to synthesize amorphous cellulose derivatives under alkaline conditions. The reactions were carried out in the presence of LiOH in ionic liquid (1-butyl-2,3-dimethylimidazolium chloride)/N,N-dimethylformamide (DMF) solvents at room temperature or 50 °C for 1 h. The Fourier transform infrared and ¹H nuclear magnetic resonance (NMR) measurements of the products supported the progress of Michael addition; however, the degrees of substitution (DS) were not high (0.3–0.6 for HEA and 0.6 for HBA). The powder X-ray diffraction analysis of the products indicated their amorphous nature. The cellulosic Michael adduct from HEA with DS = 0.6 was swollen with high polar organic liquids, such as DMF. In addition to swelling with these liquids, the cellulosic Michael adduct from HBA was soluble in dimethyl sulfoxide (DMSO), leading to its ¹H NMR analysis in DMSO-d₆. This adduct was found to form a cast film with flexible properties from its DMSO solutions. Furthermore, films containing an ionic liquid, 1-butyl-3-methylimidazolium chloride, showed thermoplasticity. The Michael addition approach to hydroxyalkyl acrylates is quite effective to totally reduce crystallinity, leading to good feasibility and processability in cellulosic materials, even with low DS. In addition, the present thermoplastic films will be applied in practical, bio-based, and eco-friendly fields. Full article

We report on the synthesis and characterization of Mn(III) chloride (Mn^IIICl₃) complexes coordinated with N-oxide ylide ligands, namely trimethyl-N-oxide (Me₃NO) and pyridine-N-oxide (PyNO). The compounds are reactive and, while isolable in the solid-state at room temperature, readily decompose into Mn(II). For example, “[Mn^IIICl₃(ONMe₃)_n]” decomposes into the 2D polymeric network compound complex salt [Mn^II(µ-Cl)₃Mn^II(µ-ONMe₃)]_n[Mn^II(µ-Cl)₃]_n·(Me₃NO·HCl)_3n (4). The reaction of Mn^IIICl₃ with PyNO forms varied Mn(III) compounds with PyNO coordination and these react with hexamethylbenzene (HMB) to form the chlorinated organic product 1-cloromethyl-2,3,4,5,6-pentamethylbenzene (8). In contrast to N-oxide coordination to Mn(III), the reaction between [Mn^IIICl₃(OPPh₃)₂] and 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) resulted in electron transfer-forming d⁵ manganate of the [TEMPO] cation instead of TEMPO–Mn(III) adducts. The reactivity affected by N-oxide coordination is discussed through comparisons with other L–Mn^IIICl₃ complexes within the context of reduction potential. Full article

A study was made on the effect of Ca, Sr, and Ba chloride complexes with dibenzo-18-crown-6 ether as catalysts on the process criteria of the efficiency of industrial cumene oxidation using kinetic modeling. It is the first stage in the process chain of polymer composite production. The kinetic scheme of the process is made of classical reactions of the radical chain mechanism (reactions of initiation, chain propagation, and chain termination), molecular reactions, reactions of formation of intermediate adducts “component of the reaction mixture—catalyst” and their decomposition, as well as reactions that take into account the specifics of the catalyst used: (1) formation of planar catalyst complexes with various substances; (2) formation of acetophenone along the catalytic path; (3) hydration of the intermediate adduct “α-methylstyrene—catalyst” to the required alcohol. It is shown that the kinetic model fully reproduces the experimental time dependencies of the cumene hydroperoxide concentration in the cumene oxidation and cumene hydroperoxide decomposition. Using the kinetic model, computational experiments were carried out, as a result of which the following conclusions were made: (1) among the considered catalysts, the complex of Sr chloride with dibenzo-18-crown-6 ether should be recognized as the best, provided that it is used at temperatures of 393–413 K and an initial concentration < 2 mmol/L; (2) to ensure selectivity comparable to the selectivity of a non-catalytic process, it is necessary to conduct the catalytic process at a lowest possible initial concentration of any of the considered catalysts. Full article

The interaction of an equilibrium mixture of monomeric and aggregated cationic trans-5,15-bis(N-methylpyridinium-4-yl)-10,15-bis-diphenylporphine (t-H₂Pagg) chloride salt with human serum albumin (HSA) has been investigated through UV/Vis absorption, fluorescence emission, circular dichroism and resonant light scattering techniques. The spectroscopic evidence reveals that both the monomeric t-H₂Pagg and its aggregates bind instantaneously to HSA, leading to the formation of a tight adduct in which the porphyrin is encapsulated within the protein scaffold (S₄₃₀) and to clusters of aggregated porphyrins in electrostatic interaction with the charged biomolecules. These latter species eventually interconvert into the final S₄₃₀ species following pseudo-first-order kinetics. Molecular docking simulations have been performed to get some insights into the nature of the final adduct. Analogously to hemin bound to HSA, the obtained model supports favorable interactions of the porphyrin in the same 1B subdomain of the protein. Hydrophobic and van der Waals energy terms are the main contributions to the calculated ΔG_bind value of −117.24 kcal/mol. Full article

The interactions of the functional additives SPS (bis-(sodium-sulfopropyl)-disulfide) and polyethylene glycol (PEG) in the presence of chloride ions were studied by time-of-flight secondary-ion mass spectrometry (TOF-SIMS) in combination with cyclic voltammetry measurements (CV). The PEG, thiolate, and chloride surface coverages were estimated and discussed in terms of their electrochemical suppressing/accelerating abilities. The conformational influence of both the gauche/trans thiolate molecules, as well as around C-C and C-O of PEG, on the electrochemical properties were discussed. The contribution of the hydrophobic interaction of -CH₂-CH₂- of PEG with chloride ions was only slightly reduced after the addition of SPS, while the contribution of Cu-PEG adducts diminished strongly. SPS and PEG demonstrated significant synergy by significant co-adsorption. It was shown that the suppressing abilities of PEG that rely on forming stable Cu-PEG adducts, identified in the form C₂H₄O₂Cu⁺ and C₃H₆OCu⁺, were significantly reduced after the addition of SPS. The major role of thiolate molecules adsorbed on a copper surface in reducing the suppressing abilities of PEG rely on the efficient capture of Cu²⁺ ions, diminishing the available copper ions for the ethereal oxygen of PEG. Full article

We report a theoretical study of the first silver-dependent enantiodivergent gold-catalysed reaction. The combination of a single chiral binuclear gold(I) chloride complex and silver perchlorate catalyses the asymmetric intramolecular hydroamination of alkenes and affords both enantiomers of the products by applying a simple solvent change from toluene to methanol. A gold-silver chloride adduct that occurs only in methanol appears to control the enantioinversion. If one gold atom coordinates and activates the alkene moiety, the other gold is included in an adduct with silver chloride, which coordinates a methanol solvent molecule and further interacts with the amine function. If the use of toluene implies free anions and affords (S)-enantiomer, methanol allows a proximal interaction with the amine, leads to an opposite stereodifferentiation of the two diastereomeric intermediates during the final protodeauration step and results in the (R)-enantiomer. Full article

Two phosphonite ligands bearing the highly sterically demanding 2,6-bis (2,6-dimethylphenyl)phenyl group (Ar^Xyl₂), PAr^Xyl₂(OPh^NO₂)₂ and PAr^Xyl₂(OPh^NO₂,Me)₂, were prepared from the parent dihalophosphines PAr^Xyl₂X₂ (X = Cl, Br) and the corresponding phenols, 4-nitrophenol and 4-nitro-2,6-dimethylphenol, respectively. DFT methods were used to examine their structural features and to determine three steric descriptors, namely the Tolman cone angle, the percentage of buried volume, and the percentage of the coordination sphere protected by the ligand. A comparison with the related terphenyl phosphines is also provided. Reactions of PAr^Xyl₂(OPh^NO₂)₂ and PAr^Xyl₂(OPh^NO₂,Me)₂ with several Pt(II) precursors were investigated, revealing a high tendency of both phosphonites to undergo C-H activation processes and generate five- or six-membered cyclometalated structures. The coordination chemistry of the new ligands was explored with isolation, among others, of three carbonyl complexes, 1-3∙CO, and the triphenylphosphine adduct 3∙PPh₃. X-ray diffraction methods permitted the determination of the solid-state structures of the mononuclear methyl carbonyl complex 1∙CO, the dinuclear chloride-bridged complex 2 and the doubly cyclometalated complex 3∙SMe₂, including the conformations adopted by the ligands upon coordination. All of the new compounds were characterized by multinuclear NMR spectroscopy in solution. Full article

Sphingolipids are essential structural components of tear film that protect the surface of the eye from dehydration. A detailed analysis of the effects of pink eye infections on the sphingolipidome in cattle has not previously been undertaken. We recently published a new assay utilizing high-resolution mass spectrometric monitoring of the chloride adducts of sphingolipids that provides enhanced sensitivity and specificity. Utilizing this assay, we monitored decreases in the levels of tear film ceramides with short-chain fatty acids, hydroxy-ceramides, phytoceramides, and hydroxy-phytoceramides. Dihydroceramide levels were unaltered and increased levels of ceramides with long-chain fatty acids (24:0 and 24:1) were monitored in cattle with pink eye. The data from this pilot study (n = 8 controls and 8 pink eye) demonstrate a major disruption of the lipid tear film layer in pink eye disease, that can result in severe eye irritation and damage. Full article

This short note describes the synthesis of an amorphous benzo[1,2,3]dithiazole chloride salt (commonly known as a ‘Herz salt’) by use of the Herz reaction. Hetero- and homolytic transformations of this species to a variety of useful adducts in medicinal and materials chemistry are well established, although there are limited examples of isolation in the literature, and characterisation data is even harder find. While several studies have confirmed the structure of the benzodithiazole ring beyond doubt, (having generated suitably crystalline salts with large counterions for XRD-analysis), there remains value in understanding and optimising the synthesis of the simple, amorphous polymorphs. For the first time, MS data is provided for this compound and a new mechanism of its formation is proposed based upon new experimental observations and data. Full article

Polar hydrophilic metabolites have been identified as important actors in many biochemical pathways. Despite continuous improvement and refinement of hydrophilic interaction liquid chromatography (HILIC) platforms, its application in global polar metabolomics has been underutilized. In this study, we aimed to systematically evaluate polar stationary phases for untargeted metabolomics by using HILIC columns (neutral and zwitterionic) that have been exploited widely in targeted approaches. To do so, high-resolution mass spectrometry was applied to thoroughly investigate selectivity, repeatability and matrix effect at three pH conditions for 9 classes of polar compounds using 54 authentic standards and plasma matrix. The column performance for utilization in untargeted metabolomics was assessed using plasma samples with diverse phenotypes. Our results indicate that the ZIC-c HILIC column operated at neutral pH exhibited several advantages, including superior performance for different classes of compounds, better isomer separation, repeatability and high metabolic coverage. Regardless of the column type, the retention of inorganic ions in plasma leads to extensive adduct formation and co-elution with analytes, which results in ion-suppression as part of the overall plasma matrix effect. In ZIC-c HILIC, the sodium chloride ion effect was particularly observed for amino acids and amine classes. Successful performance of HILIC for separation of plasma samples with different phenotypes highlights this mode of separation as a valuable approach in global profiling of plasma sample and discovering the metabolic changes associated with health and disease. Full article

Adrenaline (Adr) reacts with chlorides of Y³⁺, Ce³⁺, Nd³⁺ and Sm³⁺ in methanol at 60 °C to yield metal ion adducts of definite composition. These compounds are characterized by elemental analyses, molar conductivity, UV-Vis., ¹H–NMR, Raman laser, scanning electron microscopy, energy-dispersive X-ray spectroscopy (EDX), and mid infrared spectral measurement investigations. The adducts are found to have the formulae [Y₂(Adr)₂(H₂O)₈]Cl₃.8H₂O, [Ce(Adr)₂(H₂O)₂]Cl₃.10H₂O, [Nd(Adr)₂(H₂O)₂]Cl₃.6H₂O, and [Sm(Adr)₂(H₂O)₂]Cl₃.12H₂O, respectively. The two phenolic groups of the catechol moiety are linked to central metal ions based on the infrared and Raman laser spectra. The new compounds were tested against five gram-positive and two-gram negative bacteria, in addition to two Aspergillus strains. Metal adducts were shown to have stronger antibacterial and antifungal properties than free adrenaline compounds. Full article

The synthesis of 2-pyridyltellurenyl bromide via Br₂ oxidative cleavage of the Te–Te bond of dipyridylditelluride is reported. Single-crystal X-ray diffraction analysis of 2-pyridyltellurenyl bromide demonstrated that the Te atom of 2-pyridyltellurenyl bromide was involved in four different noncovalent contacts: Te⋯Te interactions, two Te⋯Br ChB, and one Te⋯N ChB contact forming 3D supramolecular symmetrical framework. In contrast to 2-pyridylselenenyl halides, the Te congener does not react with nitriles furnishing cyclization products. 2-Pyridylselenenyl chloride was demonstrated to easily form the corresponding adduct with benzonitrile. The cyclization product was studied by the single-crystal X-ray diffraction analysis, which revealed that in contrast to earlier studied cationic 1,2,4-selenadiazoles, here we observed that the adduct with benzonitrile formed supramolecular dimers via Se⋯Se interactions in the solid state, which were never observed before for 1,2,4-selenadiazoles. Full article

In the hydrochloride of a pyrazolyl-substituted acetylacetone, the chloride anion is hydrogen-bonded to the protonated pyrazolyl moiety. Equimolar co-crystallization with tetrafluorodiiodobenzene (TFDIB) leads to a supramolecular aggregate in which TFDIB is situated on a crystallographic center of inversion. The iodine atom in the asymmetric unit acts as halogen bond donor, and the chloride acceptor approaches the $\mathsf{\sigma }$-hole of this TFDIB iodine subtending an almost linear halogen bond, with Cl···I = $3.1653\left(11\right)$ Å and Cl···I–C = 179.32(6)°. This contact is roughly orthogonal to the N–H···Cl hydrogen bond. An analysis of the electron density according to Bader’s Quantum Theory of Atoms in Molecules confirms bond critical points (bcps) for both short contacts, with ${\rho }_{\mathrm{bcp}}$ = 0.129 for the halogen and $0.321$e${\mathrm{\AA }}^{-3}$ for the hydrogen bond. Our halogen-bonded adduct represents the prototype for a future class of co-crystals with tunable electron density distribution about the $\mathsf{\sigma }$-hole contact. Full article

Ceramides have been implicated in a number of disease processes. However, current means of evaluation with flow infusion analysis (FIA) have been limited primarily due to poor sensitivity within our high-resolution mass spectrometry lipidomics analytical platform. To circumvent this deficiency, we investigated the potential of chloride adducts as an alternative method to improve sensitivity with electrospray ionization. Chloride adducts of ceramides and ceramide subfamilies provided 2- to 50-fold increases in sensitivity both with analytical standards and biological samples. Chloride adducts of a number of other lipids with reactive hydroxy groups were also enhanced. For example, monogalactosyl diacylglycerols (MGDGs), extracted from frontal lobe cortical gray and subcortical white matter of cognitively intact subjects, were not detected as ammonium adducts but were readily detected as chloride adducts. Hydroxy lipids demonstrate a high level of specificity in that phosphoglycerols and phosphoinositols do not form chloride adducts. In the case of choline glycerophospholipids, the fatty acid substituents of these lipids could be monitored by MS² of the chloride adducts. Monitoring the chloride adducts of a number of key lipids offers enhanced sensitivity and specificity with FIA. In the case of glycerophosphocholines, the chloride adducts also allow determination of fatty acid substituents. The chloride adducts of lipids possessing electrophilic hydrogens of hydroxyl groups provide significant increases in sensitivity. In the case of glycerophosphocholines, chloride attachment to the quaternary ammonium group generates a dominant anion, which provides the identities of the fatty acid substituents under MS² conditions. Full article