Production of stable amorphous form by means of spray drying

Spray drying is a very useful method for manufacturing of amorphous solid materials. This is mainly due to the possibility of fast solvent evaporation that leads to a rapid transformation of solution to a solid state. Besides evaporation kinetics, there are various process parameters that influence physical and chemical characteristics of such obtained material. The possibility of obtaining a stable amorphous structure of the active pharmaceutical ingredient in a spray dryer was examined. A solution of the hydrochloride crystalline structure of the active pharmaceutical ingredient in a mixture of water and acetonitrile was dried at different temperatures and flowrates of nitrogen used for atomization, as well as the flowrates of the solution. The influence of the process conditions on the properties of the product was analyzed. The final dried products were characterized and identified with a variety of analytical and physical methods. The results showed that a stable amorphous structure of the high purity active pharmaceutical ingredient is obtained, and that the optimal conditions of the process are defined. The amorphous structure is stable at temperatures below 200°C when it is transformed into a new crystal structure. Conditions of high relative air humidity lead to partial transformation.     

Plane Problem for Layered Composites with Periodic Array of Interfacial Cracks Under Compressive Static Loading

The current paper addresses the problem of 2-D modelling of the onset of failure process in a layered composite with periodic array of interfacial cracks under static compression along layers. The statement of the problem is based on the most accurate approach, the model of piecewise-homogenous medium. The condition of plane strain state is considered. The shear and the extensional buckling modes are examined. The laminae are modelled by transversally isotropic material (a matrix reinforced by continuous parallel fibres). The complex non-classical failure mechanics problem is solved utilizing finite element analysis. It is found that the 0°-plies volume fraction, the crack length and the mutual position of cracks influence the critical strain in the composite.     

"If only I weren't" versus "If only I hadn't": Distinguishing shame and guilt in conterfactual thinking.

Examined the role of counterfactual thinking in 2 emotions: shame and guilt. In 1 series of studies, Ss read about situations evocative of shame and guilt or described personal experiences of guilt or shame. They then generated counterfactual alternatives to "undo" the distressing outcomes. Consistent with predictions derived from J. P. Tangney (see record 1992-05447-001), Ss tended to undo shame situations by altering qualities of the self and to undo guilt situations by altering actions. In a 2nd series of studies, Ss imagined themselves in a situation that could evoke either guilt or shame. Ss were then led to mutate the self or behavior to undo the situation. Mutation manipulations amplified shame and guilt such that the former Ss anticipated feeling greater shame, whereas the latter anticipated feeling greater guilt. The role of counterfactual thinking in specific emotions and in differentiating shame and guilt-prone personalities is discussed. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Decellularization of Human Pancreatic Fragments with Pronounced Signs of Structural Changes

A significant lack of donor organs restricts the opportunity to obtain tissue-specific scaffolds for tissue-engineering technologies. One of the acceptable solutions is the development of decellularization protocols for a human donor pancreas unsuitable for transplantation. A protocol of obtaining a biocompatible tissue-specific scaffold from decellularized fragments with pronounced human pancreas lipomatosis signs with preserved basic fibrillary proteins of a pancreatic tissue extracellular matrix was developed. The scaffold supports the adhesion and proliferation of human adipose derived stem cell (hADSCs) and prolongs the viability and insulin-producing function of pancreatic islets. Experiments conducted allow for the reliance on the prospects of using the donor pancreas unsuitable for transplantation in the technologies of tissue engineering and regenerative medicine, including the development of a tissue equivalent of a pancreas.     

Ultrahigh molecular weight polyethylene as used in articular prostheses (a molecular weight distribution study)

Currently there is widespread use of ultrahigh molecular weight polyethylene (UHMWPE) acetabular components in total joint replacement prostheses. What has been most surprising about the wear of UHMWPE under such circumstances is the occurrence of brittle fracture. Such fracture had not been observed in the usual engineering tests done in the laboratory on UHMWPE. It was only when prosthese which had been removed from patients were examined or run in hip joint simulators with serum or synovial fluid as the lubricant, that brittle fracture was encountered. The problem of environment-enhanced brittle fracture in plastics dates back to 1946. Interestingly, the phenomenon was first described in polyethylene. The prime variables involved are polymer molecular weight, sensitizing environment, stress filed, and temperature. Other things being equal, brittle behavior in polyethylene is extremely sensitive to the amount of low molecular weight polymer present. In the light of the foregoing we have studied the molecular weight distribution in six commercially available UHMWPE components. These were obtained from six different manufacturers. The specimens were characterized both on their bearing (wear) surfaces and in their interior bulk. The results obtained indicate that:

• 1 The UHMWPE components contain substantial amounts of low molecular weight polymer.
• 2 The UHMWPE components differ significantly in molecular weight distribution.
• 3 The UHMWPE components contain substantial amounts of crosslinked polymer.

     

Application of Porous Glasses in Ophthalmic Prosthetic Repair

The ophthalmic prosthetic materials besides their necessary cosmetic view should be biologically inert. Silica porous glasses can be fabricated to satisfy the cosmetic requirements while their pores can be filled with medicines that would help to avoid complications when contacting the biological tissues. In this work the ability of different silica porous glasses to support a necessary level of the medicine around itself for long periods of time was studied. Hentamicini sulphate antibiotic was used as the biologically active substance while vitamin B₆ was employed as the nutrient. The concentration of the above substances in the normal saline solution that simulated the lachrymal liquid was controlled by the luminescent technique. It was demonstrated that the silica porous glass that was obtained by phase separation at 490°C without subsequent removal of the residual silica gel supported the necessary level of medicines around itself for the longest period of time.     

Initial stages of asphaltene aggregation in dilute crude oil solutions: studies of viscosity and NMR relaxation

In crude oil-toluene solutions dynamic viscosity η and spin-spin relaxation time T₂ were measured as functions of asphaltene concentration C in the range of 10-300 mg/l. The results were supplemented by studies of optical absorption. Extrema in the measured concentration dependencies are attributed to a transient predominance of specific asphaltene aggregates—from dimers to stacked molecular nanoclusters (MNCs) of four monomers. The strikingly non-ideal properties of solutions with C below 150-170 mg/l are attributed to the strong interactions between asphaltene species. At higher C the solution properties are evidently determined by the weaker interacting MNCs and the concentration effects are closer to those in ideal fluid mixtures. The observed re-entrant η(T₂) behaviour in asphaltene solutions hypothetically has the same origin as in supercooled or demixing molecular systems, where anomalous structural and dynamical features are often explained by emerging heterogeneity due to transient spontaneous clustering.     

Creep behavior of PLA‐based biodegradable plastic exposed to a hydrocarbon liquid

This study explores the effect of hydrocarbon liquid on creep behavior of polylactic acid (PLA)‐based plastic. Evolution of the mechanical properties of the material was investigated experimentally by measurement of creep under tensile load. Tensile creep behavior was studied with a constant load over a temperature range from 30 to 50°C using specimens containing different levels of liquid. It was shown that the hydrocarbon liquid diffusion obeys the Fickian law of diffusion. The viscoelastic properties vary with temperature and these properties dramatically decrease above the glass transition temperature (T_g). Significant decreases in modulus and in the peak of tan δ were observed with an increase in liquid concentration at low temperatures. In contrast, at high temperatures, drier material recorded lower storage modulus. However, only small changes of T_g were recorded. Dependence of compliance on temperature was observed in the creep test at all levels of liquid content. With respect to drier samples, it was noted that the high liquid content material had a lower rate of increasing creep strain with temperature. Therefore, at elevated temperatures, higher creep strain of dry specimens was observed compared to those with a higher liquid content. The improvement of creep resistance and stiffening of material at high temperatures can be attributed to the significant increase of crystallinity fraction induced by liquid absorption. Understanding the effect of liquid diffusion in conjunction with temperature provides useful information for assessment of the potential use of this biodegradable plastic in load‐bearing applications exposed to an organic liquid. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Pyridinedicarboxylic Acid Diamides as Selective Ligands for Extraction and Separation of Trivalent Lanthanides and Actinides: DFT Study

This article presents a general approach to solving the urgent practical problem of separation of 4f-(lanthanides, Ln³⁺) and 5f-elements (actinides, An³⁺) very similar in properties based on the DFT quantum-chemical supercomputer simulation of Ln³⁺ and An³⁺ complexes with polydentate nitrogen-containing heterocyclic ligands. The method allows to calculate the geometry parameters of ligands and complexes and the metal to ligand binding energies with accuracy, permitting a direct comparison of calculation results with the experimental data, and estimate selectivity factors for separation of Eu³⁺/Am³⁺ model pair cations (SF_Am/Eu) in extraction experiments on a semi-quantitative level.

The applicability of the method and the approach demonstrated by DFT-modeling (nonempirical PBE functional, extended relativistic full-electron basis set) of a large series of diamides of pyridine-2,6-dicarboxylic (dipicolinic) acid (L) with different substituents at the amide nitrogen atoms and in the pyridine cycle, as well as their complexes [LM]³⁺, (H₂O)_nM(NO₃)₃ (n = 3, 4), and LM(NO₃)₃ (M = Eu, Am).

Based on the theoretical analysis a new model is proposed that describes the mechanism of Ln³⁺ and An³⁺ extraction in two-phase system highly acidic water solution-organic solvent, according to which the formation of An³⁺ and Ln³⁺ complexes occurs at the water/organic interface as a substitution reaction of hydroxonium ion in a cavity of a protonated ligand for the metal cation.

Calculation results confirm the experimentally established higher extraction ability of dipicolinic acid diamides containing one aryl and one alkyl substituent at the amide nitrogen atoms compared to the N,N,N′,N′-tetraalkyl diamides (“effect of anomalous aryl strengthening”). Based on the simulation results the structure of the modified ligand L suggested that it should ensure maximum An³⁺/Ln³separation selectivity in the series of dipicolinic acid diamides.     

Nanoparticle Synthesis by Copper (II) Acetylacetonate Vapor Decomposition in the Presence of Oxygen

Crystalline nanometer-sized Cu 2 O and CuO particle formation was studied by vapor thermal decomposition of copper (II) acetylacetonate in a vertical laminar flow reactor at ambient pressure. Experiments were carried out at 3 furnace temperature profiles (maximum values of t furn = 432, 596, 705°C) and with 2 carrier gases (oxygen/nitrogen with mixture ratios of 0.5/99.5 and 10.0/90.0). The results of computational fluid dynamics simulations are presented. The introduction of oxygen into the system was found to increase the decomposition rate and removed impurities from particles. The size of produced primary particles varied from 10 to 200 nm. Particle crystallinity was found to depend on both the oxygen concentration and the furnace temperature. A model taking into account the detailed chemical reaction mechanisms during the particle formation is proposed. The model allows one to build a dynamic phase diagram of the condensed products formed during the decomposition and is in good agreement with the experimental results.