Formation Of Linear Aggregates Research Articles

Isomerization and aggregation of 2-(2-(2-hydroxy-4-nitrophenyl)hydrazono)-1-phenylbutane-1,3-dione: Recent evidences from theory and experiment

The title compound potentially can exist as four isomers in solution. Recently Lycka has proposed a protocol for distinguishing two of them based on 15N NMR. This approach has been confirmed theoretically, in the current study, and further developed into a logical scheme that allows the existence of each of the isomers to be proven in solution. The experimental data, obtained by NMR and UV–Vis spectroscopy, have shown that the studied compound exists as a mixture of two solvent stabilized isomers in diluted solutions of dimethyl sulfoxide. However, the concentration effect also plays a substantial role allowing formation of linear aggregates as the X-ray analysis and theoretical calculations show.

The formation of linear aggregates in magnetic hyperthermia: Implications on specific absorption rate and magnetic anisotropy

The design and application of magnetic nanoparticles for use as magnetic hyperthermia agents has garnered increasing interest over the past several years. When designing these systems, the fundamentals of particle design play a key role in the observed specific absorption rate (SAR). This includes the particle's core size, polymer brush length, and colloidal arrangement. While the role of particle core size on the observed SAR has been significantly reported, the role of the polymer brush length has not attracted as much attention. It has recently been reported that for some suspensions linear aggregates form in the presence of an applied external magnetic field, i.e. chains of magnetic particles. The formation of these chains may have the potential for a dramatic impact on the biomedical application of these materials, specifically the efficiency of the particles to transfer magnetic energy to the surrounding cells. In this study we demonstrate the dependence of SAR on magnetite nanoparticle core size and brush length as well as observe the formation of magnetically induced colloidal arrangements. Colloidally stable magnetic nanoparticles were demonstrated to form linear aggregates in an alternating magnetic field. The length and distribution of the aggregates were dependent upon the stabilizing polymer molecular weight. As the molecular weight of the stabilizing layer increased, the magnetic interparticle interactions decreased therefore limiting chain formation. In addition, theoretical calculations demonstrated that interparticle spacing has a significant impact on the magnetic behavior of these materials. This work has several implications for the design of nanoparticle and magnetic hyperthermia systems, while improving understanding of how colloidal arrangement affects SAR.

Oligonucleotide Analogues with Integrated Bases and Backbones. Part 19.

AbstractThe A*[s]U(*) dinucleosides 1 and 2 form thermoreversible gels in organic solvents. The basis of the gelation is the formation of linear aggregates by base pairing following desolvation of the nucleobases. This is evidenced by the absence of gel formation by the C(6)‐deaminated analogue 3 of 1, the correlation of gelation with the anti‐conformation, as preferred for 1, and the temperature‐, concentration‐, and time‐dependent CD spectra. The gels were also characterized by the minimum gelation concentration, the gel–sol transition (melting) temperature, and rheological properties.

A study of magnetic liquids with the help of a paramagnetic sensor

The paramagnetic sensor method was used to study local magnetic fields in a magnetite aqueous suspension. The sensor was 2,2,6,6-tetramethyl-4-hydroxypiperidine-1-oxyl, a stable nitroxide radical. The lines in the EPR spectrum of the sensor were demonstrated to be broadened due to the dipole-dipole interaction with magnetite nanoparticles. It was established that no spin exchange occurred between sensor molecules and magnetite nanoparticles. The g-factor was found to decrease with the concentration of magnetite nanoparticles in the suspension. The mean strengths of the local magnetic fields calculated from changes in the EPR spectrum of the sensor proved to be substantially lower than the values determined from magnetic measurements. This difference was accounted for by the formation of linear aggregates of magnetite nanoparticles under the action of a magnetic field.

Protofibril Formation of Amyloid β-Protein at Low pH via a Non-cooperative Elongation Mechanism

Deposition of the amyloid beta-protein (Abeta) in senile or diffuse plaques is a distinctive feature of Alzheimer's disease. The role of Abeta aggregates in the etiology of the disease is still controversial. The formation of linear aggregates, known as amyloid fibrils, has been proposed as the onset and the cause of pathological deposition. Yet, recent findings suggest that a more crucial role is played by prefibrillar oligomeric assemblies of Abeta that are highly toxic in the extracellular environment. In the present work, the mechanism of protofibril formation is studied at pH 3.1, starting from a solution of oligomeric precursors. By combining static light scattering and photon correlation spectroscopy, the growth of the mass and the size of aggregates are determined at different temperatures. Analysis and scaling of kinetic data reveal that under the studied conditions protofibrils are formed via a single non-cooperative elongation mechanism, not prompted by nucleation. This process is well described as a linear colloidal aggregation due to diffusion and coalescence of growing aggregates. The rate of elongation follows an Arrhenius law with an activation enthalpy of 15 kcal mol(-1). Such a value points to a conformational change of peptides or oligomers being involved in binding to protofibrils or in general to a local reorganization of each aggregate. These results contribute to establishing a clearer relation at the molecular level between the fibrillation mechanism and fibrillar precursors. The observation of a non-cooperative aggregation pathway supports the hypothesis that amyloid formation may represent an escape route from a dangerous condition, induced by the presence of toxic oligomeric species.

Spontaneous aggregation and cytotoxicity of the beta-amyloid Abeta1-40: a kinetic model.

The time dependency of the spontaneous aggregation of the fibrillogenic beta-amyloid peptide, Abeta1-40, was measured by turbidity, circular dichroism, HPLC, and fluorescence polarization. The results by all methods were comparable and they were most consistent with a kinetic model where the peptide first slowly forms an activated monomeric derivative (AM), which is the only species able to initiate, by tetramerization, the formation of linear aggregates. The anti-Abeta antibody 6E10, raised against residues 1-17, at concentrations of 200-300 nM delayed significantly the aggregation of 50 microM amyloid peptide. The anti-Abeta antibody 4G8, raised against residues 17-24, was much less active in that respect, while the antibody A162, raised against the C-terminal residues 39-43 of the full-length Abeta was totally inactive at those concentrations. Concomitant with the aggregation experiments, we also measured the time dependency of the Abeta1-40-induced toxicity toward SH-EPI cells and hippocampal neurons, evaluated by SYTOX Green fluorescence, lactate dehydrogenase release, and activation of caspases. The extent of cell damage measured by all methods reached a maximum at the same time and this maximum coincided with that of the concentration of AM. According to the kinetic scheme, the latter is the only transient peptide species whose concentration passes through a maximum. Thus, it appears that the toxic species of Abeta1-40 is most likely the same transient activated monomer that is responsible for the nucleation of fibril formation. These conclusions should provide a structural basis for understanding the toxicity of Abeta1-40 in vitro and possibly in vivo.

Features of the Microrheological Behavior of Blood in Children

The blood of healthy children aged 2–14 was investigated. No differences between the aggregation parameters depending on the sex were revealed. In the children under the age of five, the amplitude of aggregation and the time of formation of linear aggregates were reliably lower and the strength of the largest of them and their total strength were decreased in comparison with the other age groups. An inverse correlation between the strength of the aggregates and the number of reticulocytes and leukocytes and HbA2 in the blood has been revealed.

Quantum mechanical study of molecular weight growth process by combination of aromatic molecules

Formation pathways for high-molecular-mass compound growth are presented, showing why reactions between aromatic moieties are needed to explain recent experimental findings. These reactions are then analyzed by using quantum mechanical density functional methods. A sequence of chemical reactions between aromatic compounds (e.g., phenyl) and compounds containing conjugated double bonds (e.g., acenaphthylene) was studied in detail. The sequence begins with the H-abstraction from acenaphthylene to produce the corresponding radical, which then furnishes higher aromatics through either a two-step radical-molecule reaction or a direct radical-radical addition to another aromatic radical. Iteration of this mechanism followed by rearrangement of the carbon framework ultimately leads to high-molecular-mass compounds. This sequence can be repeated for the formation of high-molecular-mass compounds. The distinguishing features of the proposed model lie in the chemical specificity of the routes considered. The aromatic radical attacks the double bond of five-membered-ring polycyclic aromatic hydrocarbons. This involves specific compounds that are exceptional soot precursors as they form resonantly stabilized radical intermediates, relieving part of the large strain in the five-membered rings by formation of linear aggregates.

Long-range attraction between colloidal spheres at the air-water interface: the consequence of an irregular meniscus

Recent observations of charged colloidal particles trapped at the air-water interface revealed long-range interparticle attractive forces, not accounted for by the standard theories of colloidal interactions. We propose a mechanism for attraction which is based on nonuniform wetting causing an irregular shape of the particle meniscus. The excess water surface area created by these distortions can be minimized when two adjacent particles assume an optimum relative orientation and distance. Typically, for spheres with diameter of 1 &mgr;m at an interparticle distance of 2 &mgr;m, deviations from the ideal contact line by as little as 50 nm result in an interaction energy of the order of 10(4)kT. Roughness-induced capillarity explains the experimental findings, including the cluster dissolution caused by addition of detergent to the subphase and the formation of linear aggregates. This kind of interaction should also be of importance in particle-stabilized foams and emulsions.