Ferrocene/ferrocenium ion as a catalyst for the photodecomposition of chloroform

Irradiation (λ > 320 nm) of ferrocene in chloroform causes decomposition of chloroform and the accumulation of HCl, CCl₃OOH, and C₂Cl₆. This appears to occur initially through a cycle in which (a) ferrocene is oxidized to ferrocenium and tetrachloroferrate ions, (b) FeCl₄ ⁻ undergoes photodissociation, and (c) ferrocenium reoxidizes the chloroferrate(II) species. On extended photolysis, the concentrations of CCl₃OOH and FeCl₄ ⁻ build up and a competing cycle in which FeCl₄ ⁻ is restored through oxidation of the chloroferrate(II) species by CCl₃OOH accelerates the decomposition rate.     

The photocatalytic decomposition of chloroform by tetrachloroaurate(III)

Abstract  

Near-UV irradiation of solutions of (Bu₄N)AuCl₄ in aerated ethanol-stabilized chloroform causes the continuous decomposition of chloroform, as evidenced by the production of many equivalents of HCl and peroxides. At the outset of irradiation, most of the AuCl₄ ⁻ is reduced to AuCl₂ ⁻, but the reduction stops and is reversed. The same experiments done in ethanol-free chloroform cause chloroform decomposition only until the irreversible reduction of the gold is complete. In deoxygenated ethanol-free chloroform, irreversible reduction to AuCl₂ ⁻ is accompanied by the formation of HCl and CCl₄, while the main decomposition products in deoxygenated ethanol-stabilized chloroform are HCl and C₂Cl₆. It is proposed that, in ethanol-free chloroform, photoreduction of AuCl₄ ⁻ begins with the concerted elimination of HCl from an association complex of CHCl₃ with AuCl₄ ⁻, and that ethanol suppresses { \textCHCl₃ ·\textAuCl₄ ^- } \{ {\text{CHCl}}_{3} \cdot {\text{AuCl}}_{4}^{ - } \} complex formation, leaving a slower radical process to carry out the photoreduction of AuCl₄ ⁻ in ethanol-stabilized chloroform. In the presence of oxygen, the radical process causes a build-up of CCl₃OOH, which reoxidizes AuCl₂ ⁻ to AuCl₄ ⁻ and allows the photodecomposition of CHCl₃ to continue indefinitely.     

Cytotoxicity and physico-chemical evaluation of acetylated and pegylated cellulose nanocrystals

The high hydrophilicity of cellulose nanocrystals (CNC) may result in poor dispersion in some matrices and solvents. So in this work, two different methodologies were used to reduce the hydrophilicity of CNC. In the first methodology, CNC were acetylated (CNC-Ac) in a mixture of acetic and hydrochloric acid, and in the second methodology, polyethylene glycol (PEG) was adsorbed onto CNC surface (CNC-PEG) under stirring in aqueous solution. CNC obtained by both methods were characterized by transmission electron microscopy (TEM), infrared spectroscopy (FTIR), X-ray diffraction (XRD), dynamic light scattering (DLS), zeta potential, and thermogravimetric analysis (TGA). Images of TEM showed that the intrinsic morphology of cellulose was preserved after both treatments. FTIR confirmed acetylation reaction by the presence of a new band at 1732 cm^?1 (acetate groups) and the consumption of OH groups. XRD showed a reduction in the crystallinity index for both applied methodologies. DLS showed reduced stability in water for CNC-Ac and CNC-PEG. Values of zeta potential changed after acetylation, from ??45 mV (CNC) to ??1 mV (CNC-Ac), and after adsorption of PEG, to ??26.7 mV (CNC-PEG). TGA showed a reduction in the thermal stability after both treatments and a change in the main degradation behavior for CNC-PEG. MTT assays showed that both proposed functionalizations induce cell proliferation, being even more evident for acetylation because, in addition to viability increase with time, it increased with the sample concentration.     

Brain T1 in young children with sickle cell disease: evidence of early abnormalities in brain development

Measurement of tissue spin lattice relaxation time (T(1)) has been used to characterize brain development in healthy children. Here we report the first study of brain T(1) in young children with sickle cell disease (SCD). The T(1) in 10 tissue samples was measured by established techniques; 46 SCD patients under the age of 4 years were compared to 267 controls, including 55 well children under the age of 4 years. A model was developed to predict the relationship between age and brain T(1) in controls, then we compared patient T(1) to healthy normal T(1). Most white matter and gray matter tissues in infant patients (<2 years old), had T(1) values significantly higher than normal. For example, 15.0% of patient caudate T(1) values were above the upper bound of the 95% confidence interval for controls, but only 2.5% of normal values are expected to be this high (p = 0.0003). Among infant patients, brain T(1) was significantly higher than normal in every tissue (p < 0.01) except cortical gray matter. However, patient T(1) values declined rapidly to values lower than normal by about age 4. Our findings imply that patients follow an abnormal developmental trajectory beginning early in infancy.     

Diversity of P450 enzymes in the biosynthesis of natural products

Covering: 1985 to 2012Diverse oxygenation patterns of natural products generated by secondary metabolic pathways in microorganisms and plants are largely achieved through the tailoring reactions catalysed by cytochrome P450 enzymes (P450s). P450s are a large family of oxidative hemoproteins found in all life forms from prokaryotes to humans. Understanding the reactivity and selectivity of these fascinating C-H bond-activating catalysts will advance their use in generating valuable pharmaceuticals and products for medicine, agriculture and industry. A major strength of this P450 group is its set of established enzyme-substrate relationships, the source of the most detailed knowledge on how P450 enzymes work. Engineering microbial-derived P450 enzymes to accommodate alternative substrates and add new functions continues to be an important near- and long-term practical goal driving the structural characterization of these molecules. Understanding the natural evolution of P450 structure-function should accelerate metabolic engineering and directed evolutionary approaches to enhance diversification of natural product structures and other biosynthetic applications.     

Dual-target sensors: the effect of the encapsulation route on pH measurements and ammonia monitoring

Six different sensors were prepared using hydrolytic and non-hydrolytic sol–gel routes and three different pH indicators as receptor elements. These materials were employed as dual-target sensors for ammonia gas sensing and pH measurements in real samples. Ultraviolet–visible diffuse reflectance spectroscopy and a colorimetric analysis were used to evaluate the pH transitions and the color change that resulted from the ammonia that was employed as a probe for gas sensing. The colorimetric analysis was performed using the CIELAB color space model with the D65 standard illuminant. The resulting $ \Updelta {\text{E}}_{\text{ab}}^{*} $ values correlated with the response time for the observation of the first visible color change detected by the human eye (N = 50), and the average time values ranged from 48 to 117 s. In addition, the response times were evaluated as a function of sample characteristics, namely, the gender, age and eye color. Only groups of these characteristics exhibited relevance to the response time and could be associated with a specific range of time. The sensors were also employed for pH measurements of an aqueous solution, and a double-color scale could be established both with the sensors synthesized by the acid route and with the pH indicators alizarin red and brilliant yellow. From this color scale, it was possible to identify a shift in the turning point of the pH indicator from the free molecule to the encapsulated molecule. The double-color scale was applied to evaluate real samples from a galvanic industry using the synthesized encapsulated sensors.     

Rapid separation of VI/VII technetium oxidation states by solvent extraction with iodonitrotetrazolium chloride

Technetium⁹⁹ poses a difficult problem at many nuclear waste disposal sites, as there have been multiple incidents of its release to the environment due to large quantities of fission products disposed in storage tanks. Tc is mostly present under two oxidation states, Tc(VII) and Tc(IV) and the separation of Tc(IV) from Tc(VII) is often crucial for laboratory-scale work performed for the study of Tc. This work offers a method for the rapid separation of Tc(IV) from Tc(VII), using a solvent extraction system containing iodonitrotetrazolium chloride and chloroform.     

On the Nitroxide Quasi‐Equilibrium in the Alkoxyamine‐Mediated Radical Polymerization of Styrene

Summary: The range of validity of two popular versions of the nitroxide quasi‐equilibrium (NQE) approximation used in the theory of kinetics of alkoxyamine mediated styrene polymerization, are systematically tested by simulation comparing the approximate and exact solutions of the equations describing the system. The validity of the different versions of the NQE approximation is analyzed in terms of the relative magnitude of (dN/dt)/(dP/dt). The approximation with a rigorous NQE, k_c[P][N] = k_d[P N], where P, N and P N are living, nitroxide radicals and dormant species respectively, with kinetic constants k_c and k_d, is found valid only for small values of the equilibrium constant K (10⁻¹¹–10⁻¹² mol · L⁻¹) and its validity is found to depend strongly of the value of K. On the other hand, the relaxed NQE approximation of Fischer and Fukuda, k_c[P][N] = k_d[P N]₀ was found to be remarkably good up to values of K around 10⁻⁸ mol · L⁻¹. This upper bound is numerically found to be 2–3 orders of magnitude smaller than the theoretical one given by Fischer. The relaxed NQE is a better one due to the fact that it never completely neglects dN/dt. It is found that the difference between these approximations lies essentially in the number of significant figures taken for the approximation; still this subtle difference results in dramatic changes in the predicted course of the reaction. Some results confirm previous findings, but a deeper understanding of the physico‐chemical phenomena and their mathematical representation and another viewpoint of the theory is offered. Additionally, experiments and simulations indicate that polymerization rate data alone are not reliable to estimate the value of K, as recently suggested.

Validity of the rigorous nitroxide quasi‐equilibrium assumption as a function of the nitroxide equilibrium constant.     

Application and Modification of Cyclometalated Ruthenium(II) Complex [Ru(o-C6H4-2-C5H4N)- (MeCN)4]PF6 for Atom Transfer Radical Polymerization

Polymerizations of n-butyl acrylate (BA), methyl methacrylate (MMA) and styrene (St) were promoted by the Ru(II) cyclometalated complex with labile MeCN ligand in the presence of Al(OiPr)₃. The polymerization proceeds via radical mechanism and requires the loss of MeCN ligand. The poor control over the polymerizations can be explained in terms of the traditional ATRP scheme. However, the controllability may be significantly improved by addition of reducing SnCl₂. Mechanism of the process is proposed.