First report on the kinetics of the uncatalyzed esterification of cellulose under homogeneous reaction conditions: a rationale for the effect of carboxylic acid anhydride chain-length on the degree of biopolymer substitution

The kinetics of the homogeneous acylation of microcrystalline cellulose, MCC, with carboxylic acid anhydrides with different acyl chain-length (Nc; ethanoic to hexanoic) in LiCl/N,N-dimethylacetamide have been studied by conductivity measurements from 65 to 85 A degrees C. We have employed cyclohexylmethanol, CHM, and trans-1,2-cyclohexanediol, CHD, as model compounds for the hydroxyl groups of the anhydroglucose unit of cellulose. The ratios of rate constants of acylation of primary (CHM; Prim-OH) and secondary (CHD; Sec-OH) groups have been employed, after correction, in order to split the overall rate constants of the reaction of MCC into contributions from the discrete OH groups. For the model compounds, we have found that k((Prim-OH))/k((Sec-OH)) > 1, akin to reactions of cellulose under heterogeneous conditions; this ratio increases as a function of increasing Nc. The overall, and partial rate constants of the acylation of MCC decrease from ethanoic- to butanoic-anhydride and then increase for pentanoic- and hexanoic anhydride, due to subtle changes in- and compensations of the enthalpy and entropy of activation.

Plasma kinetics of an LDL-like nanoemulsion and lipid transfer to HDL in subjects with glucose intolerance

OBJECTIVE: Glucose intolerance is frequently associated with an altered plasma lipid profile and increased cardiovascular disease risk. Nonetheless, lipid metabolism is scarcely studied in normolipidemic glucose-intolerant patients. The aim of this study was to investigate whether important lipid metabolic parameters, such as the kinetics of LDL free and esterified cholesterol and the transfer of lipids to HDL, are altered in glucose-intolerant patients with normal plasma lipids. METHODS: Fourteen glucose-intolerant patients and 15 control patients were studied; none of the patients had cardiovascular disease manifestations, and they were paired for age, sex, race and co-morbidities. A nanoemulsion resembling a LDL lipid composition (LDE) labeled with C-14-cholesteryl ester and H-3-free cholesterol was intravenously injected, and blood samples were collected over a 24-h period to determine the fractional clearance rate of the labels by compartmental analysis. The transfer of free and esterified cholesterol, triglycerides and phospholipids from the LDE to HDL was measured by the incubation of the LDE with plasma and radioactivity counting of the supernatant after chemical precipitation of non-HDL fractions. RESULTS: The levels of LDL, non-HDL and HDL cholesterol, triglycerides, apo A1 and apo B were equal in both groups. The 14 C-esterified cholesterol fractional clearance rate was not different between glucose-intolerant and control patients, but the H-3-free- cholesterol fractional clearance rate was greater in glucose-intolerant patients than in control patients. The lipid transfer to HDL was equal in both groups. CONCLUSION: In these glucose-intolerant patients with normal plasma lipids, a faster removal of LDE free cholesterol was the only lipid metabolic alteration detected in our study. This finding suggests that the dissociation of free cholesterol from lipoprotein particles occurs in normolipidemic glucose intolerance and may participate in atherogenic signaling.

Growth kinetics of CdS in germanium oxide glassy matrix

In the present work we revisit the size data of CdS microcrystals previously collected in the glassy matrix of Germanium oxide. The CdS clusters analyzed using electron microscopy images have shown a wurtzite structure. The mean average radius, dispersion and volume evaluated from the histograms showed good agreement for t(1/3), t(2/3) and t laws, respectively. We observed that the amount of microcrystals remains constant throughout the heat treatment process, as well as that the radii distribution has a lower limit and increases with heat treatment. The distribution of radii follows a distribution similar to the Lifshitz-Slyozov-Wagner distribution limited in the origin. Discussions led to the conclusion that the growth of CdS is a process that occurs after the fluctuating nucleation and coalescence phases. We then analyze the growth process, assuming that the evaporation is overcome by the precipitation rate, stabilizing all clusters with respect to dissolution back into the matrix. The problem was simplified neglecting anisotropy and the assuming a spherical shape for clusters and particles. The low interface tension was described in terms of an empirical potential barrier in the surface of the cluster. The growth dynamics developed considering that the number of clusters remains constant, and that the minimum size of these clusters grow with time, as the first order approximation showed a good agreement with the flaw. (C) 2012 Elsevier B.V. All rights reserved.

Thermal decomposition kinetics of Brazilian limestones: effect of CO2 partial pressure

The influence of the partial pressure of carbon dioxide (CO2) on the thermal decomposition process of a calcite (CI) and a dolomite (DP) is investigated in this paper using a thermogravimetric analyser. The tests were non-isothermal at five different heating rates in dynamic atmosphere of air with 0% and 15% carbon dioxide (CO2). In the atmosphere without CO2, the average activation energies (E-alpha) were 197.4 kJ mol(-1) and 188.1 kJ mol(-1) for CI and DP, respectively. For the DP with 15% CO2, two decomposition steps were observed, indicating a change of mechanism. The values of E-alpha for 15% CO2 were 378.7 kJ mol(-1) for the CI, and 299.8 kJ mol(-1) (first decomposition) and 453.4 kJ mol(-1) (second decomposition) for the DP, showing that the determination of E-alpha for DP should in this case be considered separately in those two distinct regions. The results obtained in this study are relevant to understanding the behaviour changes in the thermal decomposition of limestones with CO2 partial pressure when applied to technologies, such as carbon capture and storage (CCS), in which carbon dioxide is present in high concentrations.

Kinetics of thermal decomposition of niobium hydride

High-purity niobium powders can be obtained from the well-known hydride-dehydride (HDH) process. The aim of this work was the investigation of the structural phase transition of the niobium hydride to niobium metal as function of temperature, heating rate and time. The niobium powder used in this work was obtained by high-temperature hydriding of niobium machining chips followed by conventional ball milling and sieving. X-ray diffraction measurements were carried out in vacuum using a high-temperature chamber coupled to an X-ray diffractometer. During the dehydriding process, it is possible to follow the phase transition from niobium hydride to niobium metal starting at about 380 degrees C for a heating rate of 20 degrees C/min. The heating rate was found to be an important parameter, since complete dehydriding was obtained at 490 degrees C for a heating rate of 20 degrees C/min. The higher dehydriding rate was found at 500 degrees C. Results contribute to a better understanding of the kinetics of thermal decomposition of niobium hydride to niobium metal. (C) 2011 Elsevier Ltd. All rights reserved.

Thermodynamics of Axial Substitution and Kinetics of Reactions with Amino Acids for the Paddlewheel Complex Tetrakis(acetato)chloridodiruthenium(II,III)

The known paddlewheel, tetrakis(acetato)chloridodiruthenium(II,III), offers a versatile synthetic route to a novel class of antitumor diruthenium(II,III) metallo drugs, where the equatorial ligands are nonsteroidal anti-inflammatory carboxylates. This complex was studied here as a soluble starting prototype model for antitumor analogues to elucidate the reactivity of the [Ru-2(CH3COO)(4)](+) framework. Thermodynamic studies on equilibration reactions for axial substitution of water by chloride and kinetic studies on reactions of the diaqua complexes with the amino acids glycine, cysteine, histidine, and tryptophan were performed. The standard thermodynamic reaction parameters Delta H degrees, Delta S degrees, and Delta V degrees were determined and showed that both of the sequential axial substitution reactions are enthalpy driven. Kinetic rate laws and rate constants were determined for the axial substitution reactions of coordinated water by the amino acids that gave the corresponding aqua(amino acid)-Ru-2 substituted species. The results revealed that the [Ru-2(CH3COO)(4)](+) paddlewheel framework remained stable during the axial ligand substitution reactions and was also mostly preserved in the presence of the amino acids.

Plasma kinetics of an LDL-like nanoemulsion and lipid transfer to HDL in subjects with glucose intolerance

OBJECTIVE: Glucose intolerance is frequently associated with an altered plasma lipid profile and increased cardiovascular disease risk. Nonetheless, lipid metabolism is scarcely studied in normolipidemic glucose-intolerant patients. The aim of this study was to investigate whether important lipid metabolic parameters, such as the kinetics of LDL free and esterified cholesterol and the transfer of lipids to HDL, are altered in glucose-intolerant patients with normal plasma lipids. METHODS: Fourteen glucose-intolerant patients and 15 control patients were studied; none of the patients had cardiovascular disease manifestations, and they were paired for age, sex, race and co-morbidities. A nanoemulsion resembling a LDL lipid composition (LDE) labeled with 14C-cholesteryl ester and ³H-free cholesterol was intravenously injected, and blood samples were collected over a 24-h period to determine the fractional clearance rate of the labels by compartmental analysis. The transfer of free and esterified cholesterol, triglycerides and phospholipids from the LDE to HDL was measured by the incubation of the LDE with plasma and radioactivity counting of the supernatant after chemical precipitation of non-HDL fractions. RESULTS: The levels of LDL, non-HDL and HDL cholesterol, triglycerides, apo A1 and apo B were equal in both groups. The 14C-esterified cholesterol fractional clearance rate was not different between glucose-intolerant and control patients, but the ³H-free-cholesterol fractional clearance rate was greater in glucose-intolerant patients than in control patients. The lipid transfer to HDL was equal in both groups. CONCLUSION: In these glucose-intolerant patients with normal plasma lipids, a faster removal of LDE free cholesterol was the only lipid metabolic alteration detected in our study. This finding suggests that the dissociation of free cholesterol from lipoprotein particles occurs in normolipidemic glucose intolerance and may participate in atherogenic signaling.