Molybdenum(VI) Bis(imido) Complexes: From Frustrated Lewis Pairs to Weakly Coordinating Cations

Molybdenum(VI) bis(imido) complexes [Mo(NtBu)₂(L^R)₂] (R=H 1 a ; R=CF₃ 1 b ) combined with B(C₆F₅)₃ ( 1 a /B(C₆F₅)₃, 1 b /B(C₆F₅)₃) exhibit a frustrated Lewis pair (FLP) character that can heterolytically split H−H, Si−H and O−H bonds. Cleavage of H₂ and Et₃SiH affords ion pairs [Mo(NtBu)(NHtBu)(L^R)₂][HB(C₆F₅)₃] (R=H 2 a ; R=CF₃ 2 b ) composed of a Mo(VI) amido imido cation and a hydridoborate anion, while reaction with H₂O leads to [Mo(NtBu)(NHtBu)(L^R)₂][(HO)B(C₆F₅)₃] (R=H 3 a ; R=CF₃ 3 b ). Ion pairs 2 a and 2 b are catalysts for the hydrosilylation of aldehydes with triethylsilane, with 2 b being more active than 2 a . Mechanistic elucidation revealed insertion of the aldehyde into the B−H bond of [HB(C₆F₅)₃]⁻. We were able to isolate and fully characterize, including by single-crystal X-ray diffraction analysis, the inserted products Mo(NtBu)(NHtBu)(L^R)₂][{PhCH₂O}B(C₆F₅)₃] (R=H 4 a ; R=CF₃ 4 b ). Catalysis occurs at [HB(C₆F₅)₃]⁻ while [Mo(NtBu)(NHtBu)(L^R)₂]⁺ (R=H or CF₃) act as the cationic counterions. However, the striking difference in reactivity gives ample evidence that molybdenum cations behave as weakly coordinating cations (WCC).     

Impact of Matrix Metalloproteinase-9 during Periodontitis and Cardiovascular Diseases

Matrix metalloproteinase-9 (MMP-9) has been shown to play a key role in endothelial function and perhaps pivotal in the correlation between periodontal disease and cardiovascular disease (CVD). For the study, the impact of MMP-9 of periodontitis and CVD on serum and saliva concentrations was analyzed. For the study patients with periodontitis (n = 31), CVD (n = 31), periodontitis + CVD (n = 31), and healthy patients (n = 31) were enrolled. Clinical and demographic characteristics as well as serum and salivary MMP-9 were evaluated. MMP-9 concentrations in serum and saliva were statistically elevated in patients with CVD (p < 0.01) and in patients with periodontitis plus CVD (p < 0.001) compared to patients with periodontitis and healthy subjects. Multivariate regression analysis showed that c-reactive protein (hs-CRP) was the only significant predictor for MMP-9 serum (p < 0.001), whereas hs-CRP (p < 0.001) and total cholesterol (p = 0.029) were the statistically significant salivary MMP-9 predictors. This study evidenced that patients with CVD and periodontitis + CVD presented elevated MMP-9 concentrations in serum and saliva compared to patients with periodontitis and healthy subjects. Furthermore, hs-CRP was a negative predictor of serum and salivary MMP-9.     

Additional Symmetries and String Equation of the CKP Hierarchy

Based on the Orlov and Shulman’s M operator, the additional symmetries and the string equation of the CKP hierarchy are established, and then the higher order constraints on L ^l are obtained. In addition, the generating function and some properties are also given. In particular, the additional symmetry flows form a new infinite dimensional algebra , which is a subalgebra of W _1+∞.      

High‐Potential Perfluorinated Phthalocyanine–Fullerene Dyads for Generation of High‐Energy Charge‐Separated States: Formation and Photoinduced Electron‐Transfer Studies

High oxidation potential perfluorinated zinc phthalocyanines (ZnF_nPcs) are synthesised and their spectroscopic, redox, and light‐induced electron‐transfer properties investigated systematically by forming donor–acceptor dyads through metal–ligand axial coordination of fullerene (C₆₀) derivatives. Absorption and fluorescence spectral studies reveal efficient binding of the pyridine‐ (Py) and phenylimidazole‐functionalised fullerene (C₆₀Im) derivatives to the zinc centre of the F_nPcs. The determined binding constants, K, in o‐dichlorobenzene for the 1:1 complexes are in the order of 10⁴ to 10⁵ M ^?1; nearly an order of magnitude higher than that observed for the dyad formed from zinc phthalocyanine (ZnPc) lacking fluorine substituents. The geometry and electronic structure of the dyads are determined by using the B3LYP/6‐31G* method. The HOMO and LUMO levels are located on the Pc and C₆₀ entities, respectively; this suggests the formation of ZnF_nPc^.+–C₆₀Im^.? and ZnF_nPc^.+–C₆₀Py^.? (n=0, 8 or 16) intra‐supramolecular charge‐separated states during electron transfer. Electrochemical studies on the ZnPc–C₆₀ dyads enable accurate determination of their oxidation and reduction potentials and the energy of the charge‐separated states. The energy of the charge‐separated state for dyads composed of ZnF_nPc is higher than that of normal ZnPc–C₆₀ dyads and reveals their significance in harvesting higher amounts of light energy. Evidence for charge separation in the dyads is secured from femtosecond transient absorption studies in nonpolar toluene. Kinetic evaluation of the cation and anion radical ion peaks reveals ultrafast charge separation and charge recombination in dyads composed of perfluorinated phthalocyanine and fullerene; this implies their significance in solar‐energy harvesting and optoelectronic device building applications.     

Analytical theory for ion transfer–electron transfer coupled reactions at redox layer–modified/thick film–modified electrodes

Electrodes modified by liquid films or plasticized polymeric membranes containing a redox species offer valuable alternatives for the study of ion transfers and bimolecular electron transfers at liquid–liquid interfaces with conventional electrode arrangements and stable interfaces. The ion-to-electron (or electron-to-electron) transducer affects the electrochemical signal, complicating the accurate analysis of experimental data. This can be reduced through the use of an electrode surface-attached redox species of well-defined electrochemical behaviour. As will be demonstrated, the voltammetry of these systems show significant deviations with respect to individual charge transfers, which must be considered for appropriate diagnosis and quantitative analysis. For this, a simple analytical theory is presented here, deducing mathematical expressions for the current–potential response, as well as for the potential difference at the two polarized interfaces, the surface excess of the redox species and the ion interfacial concentrations.     

Probing Substrate/Catalyst Effects Using QSPR Analysis on Friedel-Crafts Acylation Reactions over Hierarchical BEA Zeolites

Attempts to optimize heterogeneous catalysis often lack quantitative comparative analysis. The use of kinetic modelling leads to rate (k) and relative sorption equilibrium constants (K), which can be further rationalized using Quantitative Structure-Property Relationships (QSPR) based on Multiple Linear Regressions (MLR). Friedel-Crafts acylation using commercial and hierarchical BEA zeolites as heterogeneous catalysts, acetic anhydride as the acylating agent, and a set of seven substrates with different sizes and chemical functionalities were herein studied. Catalytic results were correlated with the physicochemical properties of substrates and catalysts. From this analysis, a robust set of equations was obtained allowing inferences about the dominant factors governing the processes. Not entirely surprising, the rate and sorption equilibrium constants were found to be explained in part by common factors but of opposite signs: higher and stronger adsorption forces increase reaction rates, but they also make the zeolite active sites less accessible to new reactant molecules. The most relevant parameters are related to the substrates’ molecular size, which can be associated with different reaction steps, namely accessibility to micropores, diffusion capacity, and polarizability of molecules. The relatively large set of substrates used here reinforces previous findings and brings further insights into the factors that hamper/speed up Friedel-Crafts reactions in heterogeneous media.     

A Highly Selective and Sensitive Chemiluminescent Probe for Real‐Time Monitoring of Hydrogen Peroxide in Cells and Animals

Selective and sensitive molecular probes for hydrogen peroxide (H₂O₂), which plays diverse roles in oxidative stress and redox signaling, are urgently needed to investigate the physiological and pathological effects of H₂O₂. A lack of reliable tools for in vivo imaging has hampered the development of H₂O₂ mediated therapeutics. By combining a specific tandem Payne/Dakin reaction with a chemiluminescent scaffold, H₂O₂‐CL‐510 was developed as a highly selective and sensitive probe for detection of H₂O₂ both in vitro and in vivo. A rapid 430‐fold enhancement of chemiluminescence was triggered directly by H₂O₂ without any laser excitation. Arsenic trioxide induced oxidative damage in leukemia was successfully detected. In particular, cerebral ischemia‐reperfusion injury‐induced H₂O₂ fluxes were visualized in rat brains using H₂O₂‐CL‐510 , providing a new chemical tool for real‐time monitoring of H₂O₂ dynamics in living animals.     

Mycotoxins in spices and culinary herbs from Italy and Tunisia

Abstract

Spices and aromatic herbs can be contaminated with mycotoxins, since of their preharvest, postharvest, and storage conditions. In this study, 112 samples of different spices and aromatic herbs were evaluated for their mycotoxins content by HPLC-MS/MS in order to highlight their possible risk linked with human use. The results showed that mycotoxins were occasionally detected only in samples of coriander, laurel, mint, rosemary, and verbena. In both geographical origins a different contamination was detected. Among the investigated mycotoxins, AFB2, AFG1, AFG2, T2 and HT2 were detected, whereas none of the samples contained AFB1 and FB1. The co-occurrence of two toxins were observed for some samples of rosemary and verbena. This study indicates that it is essential minimize the toxins in agriculture, industry, and food-product manufacturing for the consumer health protection.     

Effect of cyclodextrins on physico-chemical and release properties of Eudragit RS 100 microparticles containing glutathione

The objective of this work was to develop a novel microparticulate system based on the mucoadhesive polymer Eudragit-RS 100 and cyclodextrins (CDs), potentially useful for the oral administration of Glutathione (γ–glutamylcysteinylglycine, GSH). For this purpose, an oil-in-oil (O/O) emulsion-solvent evaporation method was used for the preparation of microparticles (MPs) containing GSH alone or together with one of the following CDs: α-, β-, γ-, methyl-β-(Me-β-), hydroxypropyl-β-(HP-β-) or sulfobutylether-β-cyclodextrin (SBE_7m-β-CD). MPs were obtained by emulsifying a mixture of Eudragit RS 100, GSH, CD and magnesium stearate in acetone or acetonitrile with a mixture of liquid paraffin and Span 80. Size, encapsulation efficiency, and drug release of the prepared MPs were evaluated. The results clearly indicated that all the examined properties were dependent on the water-miscible solvents and CD used. In particular, MPs prepared by using acetone or acetonitrile showed different size distributions with mean diameters in the ranges 82–350 and 15–22 μm, respectively. Moreover, encapsulation efficiency values were found to be high in all cases (71–99%) and was significantly affected by the CD type. The GSH release rates were evaluated employing dissolution media with different pH values (1.2, 6.8 and 7.4) and the following rank order was obtained for MPs prepared using acetone: MPs incorporating Me-β-CD > MPs without CD > MPs incorporating the remaining CDs. On the other hand, MPs prepared using acetonitrile gave the highest GSH release rate. Finally, stability of GSH encapsulated in MPs containing HP-β-CD to enzymatic attack by pepsin A, α-chymotrypsin, and γ-glutamyltranspeptidase was also investigated.