Kinetic and Thermodynamic Studies on the Adsorption of Reactive Red 239 by Carra Sawdust Treated with Formaldehyde

In this study, carra sawdust pre-treated with formaldehyde was used to adsorb reactive red 239 (RR239). The effects of several experimental conditions, including the concentration of dye, sorbent dosage, temperature, ionic strength, stirring speed and solution pH, on the kinetics of the adsorption process have been studied, and the experimental data were fitted to pseudo-second-order model. A study of the intra-particle diffusion model indicates that the mechanism of dye adsorption using carra sawdust is rather complex and is most likely a combination of external mass transfer and intra-particle diffusion. The experimental data obtained at equilibrium were analyzed using the Langmuir and Freundlich isotherm models, and the results indicated that at this concentration range, both models can be applied for obtaining the equilibrium parameters. The maximum dye uptake obtained at 298 K was found to be 15.1 mg g(-1). In contrast to the usual systems, the reactive dye studied in the present work is strongly attached to the sawdust even after several washes with water, allowing it to be discarded as a solid waste.

Kinetic and thermodynamic investigation of Arthrospira (Spirulina) platensis fed-batch cultivation in a tubular photobioreactor using urea as nitrogen source

BACKGROUND: Fed-batch culture allows the cultivation of Arthrospira platensis using urea as nitrogen source. Tubular photobioreactors substantially increase cell growth, but the successful use of this cheap nitrogen source requires a knowledge of the kinetic and thermodynamic parameters of the process. This work aims at identifying the effect of two independent variables, temperature (T) and urea daily molar flow-rate (U), on cell growth, biomass composition and thermodynamic parameters involved in this photosynthetic cultivation. RESULTS: The optimal values obtained were T = 32 degrees C and U = 1.16 mmol L-1 d-1, under which the maximum cell concentration was 4186 +/- 39 mg L-1, cell productivity 541 +/- 5 mg L-1 d-1 and yield of biomass on nitrogen 14.3 +/- 0.1 mg mg-1. Applying an Arrhenius-type approach, the thermodynamic parameters of growth (?H* = 98.2 kJ mol-1; ?S* = - 0.020 kJ mol-1 K-1; ?G* = 104.1 kJ mol-1) and its thermal inactivation (Delta H-D(0) =168.9 kJ mol-1; Delta S-D(0) = 0.459 kJ mol-1 K-1; Delta G(D)(0) =31.98 kJ mol-1) were estimated. CONCLUSIONS: To maximize cell growth T and U were simultaneously optimized. Biomass lipid content was not influenced by the experimental conditions, while protein content was dependent on both independent variables. Using urea as nitrogen source prevented the inhibitory effect already observed with ammonium salts. Copyright (c) 2012 Society of Chemical Industry

The Ground State Energy per Site of the Quantum and Classical Edwards-Anderson Spin Glass in the Thermodynamic Limit

We derive general rigorous lower bounds for the average ground state energy per site e ((d)) of the quantum and classical Edwards-Anderson spin-glass model in dimensions d=2 and d=3 in the thermodynamic limit. For the classical model they imply that e ((2))a parts per thousand yena'3/2 and e ((3))a parts per thousand yena'2.204a <-.

DETERMINATION OF KINETIC AND THERMODYNAMIC PARAMETERS OF L-CYSTEINE ADSORPTION ONTO GOLD BY THE QCM TECHNIQUE

DETERMINATION OF KINETIC AND THERMODYNAMIC PARAMETERS OF L-CYSTEINE ADSORPTION ONTO GOLD BY THE QCM TECHNIQUE. This article discusses the adsorption kinetics of a L-cysteine monolayer onto a gold surface by means of information obtained through the QCM technique. The results indicate that the adsorption process is rapid and follows the Langmuir isotherm, in which adsorption and desorption are considered. From these measurements the following parameter values were obtained: k(d) = (4.2 +/- 0.4) x 10(-3) s(-1), k(a) = 75 +/- 6 M-1 s(-1), K-eq=(1.8 +/- 0.3) x 10(4) M-1 and Delta G(ads) = -(5.8 +/- 0.2) kcal mol(-1).

Torque removal evaluation of prosthetic screws after tightening and loosening cycles: an in vitro study

Objectives: The aim of this study was to evaluate the variation in removal torque of implant prosthetic abutment screws after successive tightening and loosening cycles, in addition to evaluating the influence of the hexagon at the abutment base on screw removal torque. Material and methods: Twenty hexagonal abutments were tightened to 20 regular external hex implants with a titanium alloy screw, with an insertion torque of 32 N cm, measured with a digital torque gauge. The implant/abutment/screw assemblies were divided into two groups: ( 1) abutments without hexagon at the base and ( 2) abutments with a hexagon at the base. Each assembly received a provisional restoration and was submitted to mechanical loading cycles. After this, the screws were removed and the removal torque was measured. This sequence was repeated 10 times, then the screw was replaced by a new one, and another cycle was performed. Linear regression analysis was performed. Results: Removal torque values tended to decrease as the number of insertion/removal cycles increased, for both groups. Comparisons of the slopes and the intercepts between groups showed no statistical difference. There was no significant difference between the mean values of last five cycles and the 11th cycle. Within the limitations of this in vitro study, it was concluded that ( 1) repeated insertion/removal cycles promoted gradual reduction in removal torque of screws, ( 2) replacing the screw with a new one after 10 cycles did not increase resistance to loosening, and ( 3) removal of the hexagon from the abutment base had no effect on the removal torque of the screws.

Evolution of time-control mechanisms in subterranean organisms: cave fishes under light-dark cycles (Teleostei: Siluriformes, Characiformes)

Subterranean organisms are excellent models for chronobiological studies, yet relatively few taxa have been investigated with this focus. Former results were interpreted as a pattern of regression of circadian locomotor activity rhythms in troglobitic (exclusively subterranean) species. In this paper we report results of experiments with cave fishes showing variable degrees of troglomorphism (reduction of eyes, melanic pigmentation and other specializations related to the hypogean life) submitted to light-dark cycles, preceded and followed by several days in constant darkness. Samples from seven species have been monitored in our laboratory for the detection of significant circadian rhythms in locomotor activity: S. typhlops, an extremely troglomophic species, presented the lowest number of significant components in the circadian range (only one individual out of eight in DD1 and three other fish in LD), all weak (low values of spectral power). Higher incidence of circadian components was observed for P. kronei - only one among six studied catfish without significant circadian rhythms under DD1 and DD2; spectral powers were generally high. Intermediate situations were observed for the remaining species, however all of them presented relatively strong significant rhythms under LD. Residual oscillations (circadian rhythms in DD2) were detected in at least part of the studied individuals of all species but S. typhlops, without a correlation with spectral powers of LD rhythms, i.e., individuals exhibiting residual oscillations were not necessarily those with the strongest LD rhythms. In conclusion, the accumulated evidence for troglobitic fishes strongly supports the hypothesis of external, environmental selection for circadian locomotor rhythms.

Interaction between bradykinin potentiating nonapeptide (BPP9a) and beta-cyclodextrin: A structural and thermodynamic study

Herein, we demonstrate the physical and chemical characterizations of the supramolecular complex formed between beta-cyclodextrin (beta CD) and bradykinin potentiating nonapeptide (BPP9a), an endogenous toxin found in Bothrops jararaca. Circular dichroism results indicate a conformational change in the BPP9a secondary structure upon its complexation with beta CD. Nuclear magnetic resonance results, mainly from NOESY experiments, and theoretical calculations showed a favorable interaction between the tryptophan residue of BPP9a and the beta CD cavity. Thermodynamic inclusion parameters were investigated by isothermal titration calorimetry, demonstrating that beta CD/BPP9a complex formation is an exothermic process that results in a reduction in entropy. Additionally, in vitro degradation study of BPP9a against trypsin (37 degrees C, pH 7.2) showed higher stability of peptide in presence of beta CD. This beta CD/BPP9a complex, which presents new chemical properties arising from the peptide inclusion process, may be useful as an antihypertensive drug in oral pharmaceutical formulations. (C) 2011 Elsevier B.V. All rights reserved.

Low-temperature thermodynamic properties near the field-induced quantum critical point in NiCl2-4SC(NH2)(2)

We present a comprehensive experimental and theoretical investigation of the thermodynamic properties: specific heat, magnetization, and thermal expansion in the vicinity of the field-induced quantum critical point (QCP) around the lower critical field H-c1 approximate to 2 T in NiCl2-4SC(NH2)(2). A T-3/2 behavior in the specific heat and magnetization is observed at very low temperatures at H = H-c1, which is consistent with the universality class of Bose-Einstein condensation of magnons. The temperature dependence of the thermal expansion coefficient at H-c1 shows minor deviations from the expected T-1/2 behavior. Our experimental study is complemented by analytical calculations and quantum Monte Carlo simulations, which reproduce nicely the measured quantities. We analyze the thermal and the magnetic Gruneisen parameters, which are ideal quantities to identify QCPs. Both parameters diverge at H-c1 with the expected T-1 power law. By using the Ehrenfest relations at the second-order phase transition, we are able to estimate the pressure dependencies of the characteristic temperature and field scales.

Flavonoid interactions with human transthyretin: Combined structural and thermodynamic analysis

Transthyretin (TTR) is a carrier protein involved in human amyloidosis. The development of small molecules that may act as TTR amyloid inhibitors is a promising strategy to treat these pathologies. Here we selected and characterized the interaction of flavonoids with the wild type and the V30M amyloidogenic mutant TTR. TTR acid aggregation was evaluated in vitro in the presence of the different flavonoids. The best TTR aggregation inhibitors were studied by Isothermal Titration Calorimetry (ITC) in order to reveal their thermodynamic signature of binding to TTRwt. Crystal structures of TTRwt in complex with the top binders were also obtained, enabling us to in depth inspect TTR interactions with these flavonoids. The results indicate that changing the number and position of hydroxyl groups attached to the flavonoid core strongly influence flavonoid recognition by TTR, either by changing ligand affinity or its mechanism of interaction with the two sites of TTR. We also compared the results obtained for ITRwt with the V30M mutant structure in the apo form, allowing us to pinpoint structural features that may facilitate or hamper ligand binding to the V30M mutant. Our data show that the TTRwt binding site is labile and, in particular, the central region of the cavity is sensible for the small differences in the ligands tested and can be influenced by the Met30 amyloidogenic mutation, therefore playing important roles in flavonoid binding affinity, mechanism and mutant protein ligand binding specificities. (C) 2012 Elsevier Inc. All rights reserved.

Millennial-scale climate cycles in Permian-Carboniferous rhythmites: Permanent feature throughout geologic time?

Two late Paleozoic glacial rhythmite successions from the Itarare Group (Parana Basin, Brazil) were examined for paleoclimate variations. Paleomagnetic (characteristic remanent magnetization, ChRM) and magnetic susceptibility (K(z)) measurements taken from the rhythmites are interpreted as paleoclimatic proxies. Ratios of low-frequency components in the K(z) variations suggest Milankovitch periodicities; this leads to recognition of other, millennial-scale variations reminiscent of abrupt climate changes during late Quaternary time, and are suggestive of Bond cycles and the 2.4 k.y. solar cycle. We infer from these patterns that millennial-scale climate change is not restricted to the Quaternary Period, and that millennial forcing mechanisms may have been prevalent throughout geologic time.

Storage of bovine reproductive tissues and RNA extracts on ice for 24h or repeated freeze–thaw cycles do not affect RNA integrity

The aims of this study were to test (i) the effect of time of tissue and RNA extracts storage on ice and (ii) the effect of repeated freeze–thaw cycles on RNA integrity and gene expression of bovine reproductive tissues. Fragments of endometrium (ENDO), corpus luteum (CL) and ampulla (AMP) were subdivided and incubated for 0, 1, 3, 6, 12 or 24 h on ice. RNA extracts were incubated on ice for 0, 3, 12 or 24 h, or exposed to 1, 2, 4 or 6 freeze–thaw cycles. RNA integrity number (RIN) was estimated. Expression of progesterone receptor (PGR) and cyclophilin genes from RNA extracts stored on ice for 0 or 24 h, and 1 or 6 freeze–thaw cycles was measured by qPCR. Tissue and RNA extract incubation on ice, and repeated freeze–thaw cycles did not affect RIN values of RNA from ENDO, CL or AMP. Storage on ice or exposure to freeze–thaw cycles did not affect Cq values for PGR or cyclophilin genes. In conclusion, neither generalized RNA degradation nor specific RNA degradation was affected by storage of tissue or RNA extracts on ice for up to 24 h, or by up to 6 freeze–thaw cycles of RNA extracts obtained from bovine ENDO, CL and AMP.