Visible Light Sensitized CO2 Activation by the Tetraaza [Co^(II)N_4H(MeCN)]^(2+) Complex Investigated by FT-IR Spectroscopy and DFT Calculations

In situ FT-IR measurements and electronic structure calculations are reported for the reduction of CO_2 catalyzed by the macrocyclic complex [Co^(II)N_4H]^(2+) (N_4H = 2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(17),2,11,13,15-pentaene). Beginning from the [Co^(II)N_4H]^(2+) resting state of the complex in wet acetonitrile solution, two different visible light sensitizers with substantially different reducing power are employed to access reduced states. Accessing reduced states of the complex with a [Ru(bpy)_3]^(2+) sensitizer yields an infrared band at 1670 cm^(–1) attributed to carboxylate, which is also observed for an authentic sample of the one-electron reduced complex [CoN_4H(MeCN)]^+ in CO_2 saturated acetonitrile solution. The results are interpreted based on calculations using the pure BP86 functional that correctly reproduces experimental geometries. Continuum solvation effects are also included. The calculations show that Co is reduced to Co^I in the first reduction, which is consistent with experimental d–d spectra of square Co(I) macrocycle complexes. The energy of the CO_2 adduct of the one-electron reduced catalyst complex is essentially the same as for [CoN_4H(MeCN)]^+, which implies that only a fraction of the latter forms an adduct with CO_2. By contrast, the calculations indicate a crucial role for redox noninnocence of the macrocyclic ligand in the doubly reduced state, [Co^I(N_4H) –•], and show that [Co^I(N_4H) –•] binds partially reduced CO_2 fairly strongly. Experimentally accessing [Co^I(N_4H) –•] with an Ir(bpy)_3 sensitizer with greater reducing power closes the catalytic cycle as FT-IR spectroscopy shows CO production. Use of isotopically substituted C^(18)O_2 also shows clear evidence for ^(18)O-substituted byproducts from CO_2 reduction to CO

Changes in the ceIl membrane of Lactobacillus bulgaricus during storage following freeze-drying

The mechanism of inactivation of freeze-dried Lactobacillus bulgaricus during storage in maltodextrin under controlled humidity was investigated. Evidence is presented supporting the hypothesis that membrane damage occurs during storage. A study on the lipid composition of the cells by gas chromatography showed a decrease in the unsaturated and saturated fatty acid content of the cell. Further evidence indicating membrane damage includes a decrease in membrane bound proton-translocating ATPase activity

Mechanistic evaluation of primary human hepatocyte culture using global proteomic analysis reveals a selective dedifferentiation profile

© 2016 The Author(s)The application of primary human hepatocytes following isolation from human tissue is well accepted to be compromised by the process of dedifferentiation. This phenomenon reduces many unique hepatocyte functions, limiting their use in drug disposition and toxicity assessment. The aetiology of dedifferentiation has not been well defined, and further understanding of the process would allow the development of novel strategies for sustaining the hepatocyte phenotype in culture or for improving protocols for maturation of hepatocytes generated from stem cells. We have therefore carried out the first proteomic comparison of primary human hepatocyte differentiation. Cells were cultured for 0, 24, 72 and 168 h as a monolayer in order to permit unrestricted hepatocyte dedifferentiation, so as to reveal the causative signalling pathways and factors in this process, by pathway analysis. A total of 3430 proteins were identified with a false detection rate of <1 %, of which 1117 were quantified at every time point. Increasing numbers of significantly differentially expressed proteins compared with the freshly isolated cells were observed at 24 h (40 proteins), 72 h (118 proteins) and 168 h (272 proteins) (p < 0.05). In particular, cytochromes P450 and mitochondrial proteins underwent major changes, confirmed by functional studies and investigated by pathway analysis. We report the key factors and pathways which underlie the loss of hepatic phenotype in vitro, particularly those driving the large-scale and selective remodelling of the mitochondrial and metabolic proteomes. In summary, these findings expand the current understanding of dedifferentiation should facilitate further development of simple and complex hepatic culture systems

Infrared study of the silica/silane reaction

International audienceThe silica-silane system is used in modern tire tread compounds to improve wet grip and rolling resistance. An efficient silica / silane coupling during the mixing process is necessary to achieve the required in-rubber-properties. In order to understand this coupling reaction in detail, the silanol group density of the silica was characterized in depth. Furthermore, the reaction of a mercapto silane (Si 263 (R)) with two different silicas was studied with special infrared (IR) techniques. The infrared spectrum of the v (SiOH) region shows the behavior of SiOH groups during the reaction and contributes to clarify their role in the silane grafting reaction

Insight into methanol photooxidation over mono- (Au, Cu) and bimetallic (AuCu) catalysts supported on niobium pentoxide — An operando-IR study

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