Light scattering studies of copolymers. 1. Soluble hemoglobin--dextran complexes

Complexes between dextrans of different molar mass and bovine hemoglobin were synthesized by two different methods. In the alkylation method three and in the dialdehyde method, two hemoglobins are coupled on average to one dextran molecule. In both cases, the soluble hemoglobin-dextran complexes reversibly bind and release oxygen; the oxygen affinity is greater than that of free hemoglobin. Static and dynamic light scattering was used to determine the average molar mass M_u, the radius of gyration 〈S〉, and the hydrodynamic radius R_h of both the complexes and the single dextrans. Interpretation of these data is complicated due to the fact that the complexes are copolymers. When appropriate approximations are made, the results indicate that the complexes have a spherical shape and an internal structure of a multiple-chain network, where several dextrans are linked together by the hemoglobins. The number of single dextrans per complex increases as the molar mass of the single dextrans is decreased. The increment is greater in the dialdehyde than in the alkylation method. The probable reason is that in the dialdehyde method one hemoglobin can connect many dextrans simultaneously while in the alkylation method a hemoglobin is able to link maximally two dextrans. The ratio of the radius of gyration to the hydrodynamic radius decreases as the temperature is increased. This suggests a decrease of the solvent penetration length for the complexes and can be interpreted on the basis of the Deutsch-Felderhof theory for porous spheres. © 1994 John Wiley & Sons, Inc.     

(Z)-3-p-tolylsulfinylacrylonitrile as a chiral dienophile: diels-alder reactions with furan and acyclic dienes

The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.     

Preparation of HMWCNT/PLLA nanocomposite scaffolds for application in nerve tissue engineering and evaluation of their physical,mechanical and cellular activity properties

This study was aimed to prepare biodegradable and porous nanocomposite scaffolds with microtubular orientation structure as a model for nerve tissue engineering by thermally induced phase separation (TIPS) method using dioxane as the solvent, crystalline poly (L‐lactic acid) (PLLA) and multi‐walled carbon nanotubes (MWCNTs). In order to overcome dispersion of MWCNTs in the PLLA matrix, heparinization of MWCNTs was performed. Solvent crystallization, oriented structure, the mean pore diameter and porosity percentage of the scaffolds were controlled by fundamental system parameters including temperature‐gradient of the system, polymer solution concentration and carbon nanotube content. Scanning Electron Microscopy (SEM), ImageJ, software and dynamic mechanical thermal analysis (DMTA) were used to investigate the structural and mechanical properties. TEM observation was carried out for characterization of nanotube dispersion in PLLA. It was found that the scaffolds containing heparinized multi‐walled carbon nanotubes (HMWCNTs) exhibited higher storage modulus, better carbon nanotube (CNT) dispersion and tubular orientation structure than those with non heparinized MWCNTs. In‐vitro studies were also conducted by using murine P₁₉ cell line as a suitable model system to analyze neuronal differentiation over a 2‐week period. Immunofluorescence and DAPI staining were used to confirm the cells' attachment and differentiation on the PLLA/HMWCNT nanocomposite scaffolds. Based on the results, we can conclude that the PLLA/HMWCNT scaffolds enhanced the nerve cell differentiation and proliferation, and therefore, acted as a positive cue to support neurite outgrowth. Copyright © 2015 John Wiley & Sons, Ltd.     

A simple one-pot procedure for the direct conversion of alcohols into azides using TsIm

A facile and efficient method for one-pot conversion of alcohols into azides using N-(p-toluenesulfonyl)imidazole (TsIm) is described. In this method, alcohols are refluxed with a mixture of NaN₃, TsIm and triethylamine in the presence of catalytic amounts of tetra-n-butylammonium iodide (TBAI) in DMF affording the corresponding alkyl azides in good yields. This methodology is highly efficient for various structurally diverse alcohols with selectivity for ROH: 1° > 2° > 3°.     

Copper/Graphene/Clay Nanohybrid: A Highly Efficient Heterogeneous Nanocatalyst for the Synthesis of Novel 1,2,3‐Triazolyl Carboacyclic Nucleosides via ‘Click’ Huisgen 1,3‐Dipolar Cycloaddition

A very mild and highly efficient synthesis of some novel 1H‐1,2,3‐triazolyl carboacyclic nucleosides via a ‘Click’ Huisgen cycloaddition of N‐propargyl nucleobases and azido alcohols using Cu/aminoclay/reduced graphene oxide nanohybrid (Cu/AC/r‐GO nanohybrid) as nanocatalyst is described. The preparation and characterization of Cu/AC/r‐GO nanohybrid are discussed. This catalyst was characterized by X‐ray diffraction, FT‐IR, TEM, and energy‐dispersive analysis of X‐ray techniques. Cu/AC/r‐GO nanohybrid is a stable and highly efficient heterogeneous nanocatalyst that can be easily prepared, used, and restored from the reaction mixture by simple filtration, and reused for many consecutive trials without significant decrease in activity.     

Rare-earth metal dichloride and bis(alkyl) complexes containing amidinate-amidopyridinate ligands: synthesis,structure, and reactivity

A reaction of anhydrous yttrium chloride with an equimolar amount of lithium amidinateamidopyridinate obtained in situ by metallation of N,N’-bis(2,6-dimethylphenyl)-N-{6-[(2,6-dimethylphenyl)amino]pyridin-2-yl}acetimidamide ((2,6-Me₂C₆H₃)NH(2,6-C₆H₃N)N(2,6-Me₂C₆H₃)C(Me)=N(2,6-Me₂C₆H₃), L¹H) (1) with n-butyllithium in THF at–70 °C was used to synthesize the yttrium dichloride complex (L¹)YCl₂(THF)₂ (2). The lutetium bis(alkyl) complex, namely, N’-(2,6-diisopropylphenyl)-N-(2,6-dimethylphenyl-N-{6-[(2,6-dimethylphenyl)amido]pyridin-2-yl}acetimidoamidinatebis(trimethylsilylmethyl)lutetium (4), was obtained by the reaction of N’-(2,6-diisopropylphenyl)-N-(2,6-dimethylphenyl)-N-(6-((2,6dimethylphenyl)amino)pyridin-2-yl)acetimidamide ((2,6-Me₂C₆H₃)NH(2,6-C₆H₃N)N-(2,6-Me₂C₆H₃)C(Me)=N(2,6-Pr ₂ ⁱ C₆H₃), L²H (3)) with an equimolar amount of Lu(CH₂SiMe₃)₃(THF)₂. Complex 4 was found to be very stable and did not show indications of C—H-activation and other kinds of disintegration in benzene or toluene solution even upon prolonged heating at 60 °C. The reaction of complex 4 with an equimolar amount of 2,6-diisopropylaniline in toluene solution at room temperature led to the formation of the lutetium alkyl-anilide complex (L²)Lu(CH₂SiMe₃)(NH-2,6-Pr ₂ ⁱ C₆H₃) (5). A three-component system 4—AlBu ₃ ⁱ —[X][B(C₆F₅)₄] ([X] = [Ph₃C], [PhNHMe₂], the molar ratio of 1: 10: 1) was found to catalyze polymerization of isoprene.     

Theoretical investigation of effects of local cooling of a nozzle divergent section for controlling condensation shock in a supersonic two-phase flow of steam

In supersonic adiabatic two-phase flows of steam, under the influence of supersonic acceleration, the fluid loses its equilibrium conditions and becomes supersaturated. Following this condition and to restore the fluid to equilibrium, micro droplets of water form in the absence of any surface or foreign particles. This phenomenon is called homogeneous nucleation and the formed minute small droplets grow along the fluid flow path. The formation of these droplets and their growth causes the release of the latent heat of evaporation to the gas phase particularly in the nucleation region, and results in an increase in the flow pressure which is called the condensation shock. In this paper, and in continuation of the series of papers by the authors, in addition to analytically solving the adiabatic gas-liquid supersonic flow of steam in a convergent-divergent channel, a novel solution to controlling the undesired effects of this pressure rise (condensation shock) is presented. In the proposed method, with the help of cooling the divergent section of the nozzle, the analytical model for the 1D non-adiabatic two-phase steam flows is further developed which shows considerable decrease in the intensity of the formed condensation shock. Also the growth rate of the formed droplets due to the cooling of the steam flow has higher importance than the nucleation itself.     

Two and k-Photon Jaynes–Cummings Models and Dirac Oscillator Problem in Bargmann–Segal Representation

In this work, we show that the Bargmann–Segal representation is a very simple approach to obtain the energy eigenvalues of some two-level quantum systems. It is shown that for 2-photon and k-photon Jaynes–Cummings models, the Bargmann–Segal realization gives the same energy eigenvalue which obtained by Lie algebraic and the matrix methods. We also study the Dirac oscillator problem in this representation.     

Narrow band quantitative and multivariate electroencephalogram analysis of peri-adolescent period

ABSTRACT: BACKGROUND: The peri-adolescent period is a crucial developmental moment of transition from childhood to emergent adulthood. The present report analyses the differences in Power Spectrum (PS) of the Electroencephalogram (EEG) between late childhood (24 children between 8 and 13 years old) and young adulthood (24 young adults between 18 and 23 years old). RESULTS: The narrow band analysis of the Electroencephalogram was computed in the frequency range of 0--20 Hz. The analysis of mean and variance suggested that six frequency ranges presented a different rate of maturation at these ages, namely: low delta, delta-theta, low alpha, high alpha, low beta and high beta. For most of these bands the maturation seems to occur later in anterior sites than posterior sites. Correlational analysis showed a lower pattern of correlation between different frequencies in children than in young adults, suggesting a certain asynchrony in the maturation of different rhythms. The topographical analysis revealed similar topographies of the different rhythms in children and young adults. Principal Component Analysis (PCA) demonstrated the same internal structure for the Electroencephalogram of both age groups. Principal Component Analysis allowed to separate four subcomponents in the alpha range. All these subcomponents peaked at a lower frequency in children than in young adults. CONCLUSIONS: The present approaches complement and solve some of the incertitudes when the classical brain broad rhythm analysis is applied. Children have a higher absolute power than young adults for frequency ranges between 0-20 Hz, the correlation of Power Spectrum (PS) with age and the variance age comparison showed that there are six ranges of frequencies that can distinguish the level of EEG maturation in children and adults. The establishment of maturational order of different frequencies and its possible maturational interdependence would require a complete series including all the different ages.     

Microleakage and antibacterial properties of ZnO and ZnO:Ag nanopowders prepared via a sol–gel method for endodontic sealer application

A novel method, recently proved useful for the synthesis of nanoparticles, has been now used for the preparation of very stable silver iodide–trihexyl(tetradecyl)phosphonium chloride ionanofluids. Only the ionic liquid and the AgI bulk powder were needed. Synthesized nanofluids are much more stable than those obtained by simple dispersion of the nanoparticles in the base fluid. The ionanofluids were synthesized at different concentrations (up to 50 % w/w) and characterized in terms of physical, electrical, and thermal properties (density, viscosity, refractive index, electric conductivity, and specific heat capacity). A very high increase in the electric conductivity of the base ionic liquid was expected due to the high concentration of nanoparticles achieved. Nonetheless, it was not found, probably due to the reduction of ions mobility caused by the increase of the viscosity in ionanofluids with concentrations over 20 % w/w. An appropriate characterization of nanoparticles composing the nanofluids was carried out (UV–Vis absorbance, shape and size distribution). The diameter of the particles was measured and calculated by different techniques and approximations, obtaining a value of 2–4 nm. They were spherical, well-defined, and not agglomerated, with a narrow size distribution. The X-ray powder diffraction confirmed that no structural change took place in the transformation of the bulk solid to nanoparticles.