Selective Complexation of Hydrazone Based Ketimine with 3d, 4d,and 5d Metals: Synthesis,Characterization, and Biological Activity

Russian Journal of General Chemistry - The hydrazone derived ketimine of dehydroacetic acid and its metal {Cu(II), Ni(II), Zn(II), Fe(III), Cd(II), Pd(II), La(III), Nd(III), Ce(III)} complexes are...     

Ultrasonic-assisted manufacturing processes: variational model and numerical simulations

We present a computational study of ultrasonic assisted manufacturing processes including sheet metal forming, upsetting, and wire drawing. A fully variational porous plasticity model is modified to include ultrasonic softening effects and then utilized to account for instantaneous softening when ultrasonic energy is applied during deformation. Material model parameters are identified via inverse modeling, i.e. by using experimental data. The versatility and predictive ability of the model are demonstrated and the effect of ultrasonic intensity on the manufacturing process at hand is investigated and compared qualitatively with experimental results reported in the literature.     

Pregnane derivatives from Potentilla evestita

A new pregnane derivative, 2,6beta,7beta-trihydroxy-4-methyl-19-norpregna-1,3,5(10)-trien-17-one, has been isolated from the ethyl acetate soluble fraction of Potentilla evestita along with a pregnane derivative, 11alpha,17alpha,21-trihydroxypregna-4,16(22)-diene-3,20-dione, that is reported for the first time as a natural product. Their structures were elucidated with the aid of 1H and 13C NMR spectra and by COSY, HMQC, HMBC and NOESY experiments.     

Properties of Phosphoric Acid Doped Poly（benzimidazole/sulfone/siloxane/amide）/Sulfonated Polystyrene/Silica Nanoparticle-based Proton Exchange Membranes for Fuel Cells

New siloxane and sulfone containing poly(benzimidazole/sulfone/siloxane/amide)(PBSSA) has been prepared for the formation of hybrid membranes(PBSSA/PS-S/SiNPs) with sulfonated polystyrene(PS-S) and 0.1 wt%-2 wt% silica nanoparticles(SiNPs). Field emission scanning electron micrographs showed good dispersion of filler, formation of dense nanoporous honeycomb like structure and uniform ionic pathway in these hybrids. The porous membrane structure was responsible for the fine water retention capability and higher proton conductivity of the new hybrids. Increasing the amount of nanoparticles from 0.1 wt% to 2 wt% increased the tensile stress of acid doped PBSSA/PS-S/SiNPs nanocomposites from 65.7 MPa to 68.5 MPa. A relationship between nanofiller loading and thermal stability of the membranes was also experientially studied, as the glass transition temperature of phosphoric acid doped PBSSA/PS-S/SiNPs nanocomposites increased from 207 °C to 215 °C. The membranes also had higher ion exchange capacity(IEC) around 2.01 mmol/g to 3.01 mmol/g. The novel membranes with high IEC value achieved high proton conductivity of 1.10-2.34 S/cm in a wide range of humidity values at 80 °C which was higher than that of perfluorinated Nafion 117 membrane(1.1 × 10-1 S/cm) at 80 °C(94% RH). A H2/O2 fuel cell using the PBSSA/PS-S/SiNP 2(IEC 3.01 mmol/g) showed better performance than that of Nafion 117 at 40 °C and 30% RH.     

Synthesis,Characterization, and Silver Nanoparticles Fabrication in N-isopropylacrylamide-Based Polymer Microgels for Rapid Degradation of p-Nitrophenol

Multiresponsive poly(N-isopropylacrylamide-co-methacrylic acid) microgels were synthesized by precipitation polymerization in aqueous medium. Then silver-poly(N-isopropylacrylamide-co-methacrylic acid) hybrid microgels were prepared by in-situ reduction of silver ions. Formation of microgels was confirmed by Fourier transform infrared spectroscopic analysis. pH and temperature sensitivity of microgel was studied by dynamic light scattering. Hydrodynamic radius of microgels decreases with increase in temperature at pH 8.20 and show volume phase transition temperature around 45°C. At pH 2.65, hydrodynamic radius decreases with increase in temperatures upto 35°C but further increase in temperature causes aggregation and microgel becomes unstable due to increase of hydrophobicity. With increase in pH of medium, the hydrodynamic radius of microgels increases sigmoidally. Formation of silver nanoparticles inside microgel and pH dependence of surface plasmon resonance wavelength of the hybrid microgels were investigated by ultraviolet-visible spectroscopy. The value of surface plasmon resonance band and absorbance associated with surface plasmon resonance band increases with increases in pH of the medium. The apparent rate constant of reduction of p-nitrophenol was found to be linearly dependent on volume of hybrid microgels used as catalyst. The system has a potential to be used as effective catalyst for rapid degradation of industrial pollutant.     

Role of Cloud Point of the Capping Agent (Nonionic Surfactant,Triton X-100) on the Synthesis of Silver Nanoparticles

The solution behavior of the nonionic surfactants below and above the cloud point (CP) is quite different. Below CP, a single phase of molecular or micellar solution exists, whereas above the CP, the solution separates into two phases: the first one is denser and smaller phase and contains most of the surfactant and the other one is relatively a voluminous aqueous phase and has surfactant concentration close to the critical micelle concentration (cmc). There are many reports available where nonionic surfactant is used as capping agent. But, to the best of our knowledge, there is no report on the CP's role on the synthesis of nanoparticles (NPs). Therefore, it is very important to understand the role of the CP on the synthesis of NPs. In the present work, we report the role of the clouding of the nonionic surfactant Triton X-100 (using as capping agent) on the synthesis of AgNPs below and above the CP. The morphology of AgNPs was studied by transmission electron microscopy (TEM), dynamic light scattering (DLS), UV–Vis absorption, etc., techniques. Below the CP, spherical polydisperse particles of 12 ± 5 nm mean diameter were found, whereas above the CP, the aggregated particles with higher diameter were found.     

The Micellization and Clouding Phenomena of a Nonionic Surfactant,Poly(ethylene glycol) t-octylphenyl ether (Triton X-100): Effect of (Chloride Salt) Electrolytes

Herein, we report the micellization and the clouding of a nonionic surfactant, poly(ethylene glycol) t-octylphenyl ether (Triton X-100), in aqueous solutions in the absence and presence of (chloride salt) electrolytes. In the absence and presence of electrolytes, the critical micelle concentration (CMC) of Triton X-100 was measured by surface tension measurements. Upon increasing the temperature as well as the concentration of electrolytes, the CMCs decreased. The surface properties and the thermodynamic parameters of the micellar systems were evaluated. From these evaluated thermodynamic parameters, it was found that in the presence of an electrolyte, the stability of the micellar system is high. The cloud points (CPs) of Triton X-100 were also measured in the absence and presence of metallic ions of electrolytes. Upon the addition of metallic ions of chloride salts (electrolytes), the decrease in CP values was observed and the order was found to be: K⁺ > Na⁺ > Li⁺ > NH⁺₄.     

Modification of the thermal unfolding pathways of myoglobin upon drug interaction in different aqueous media

In this work, we have analyzed the influence of two structurally related phenothiazine drugs, promazine and triflupromazine hydrochlorides, when bound to myoglobin, a model protein, and how the drug concentration and solution conditions may affect the denaturation process of this protein. In this manner, we derive the thermodynamic quantities of the unfolding process by using a spectroscopic technique such as UV-vis spectroscopy at different drugs concentrations and at pH 2.5, 5.5, and 9.0. To do this, a thermodynamic model was used which included experimental data corresponding to the pre- and post-transition into the observable transition. It has been found that both drugs play a destabilizing role for the protein, at least at low concentrations. In addition, at acidic pH and higher drug concentrations, a stabilizing effect can be observed, which may be related to the formation of some type of protein refolding, subsequent aggregation, or both. The reason for this behavior has been suggested to be the different protein conformations at acidic pH, the increase of solvent-exposed hydrophobic and hydrophilic residues after denaturation and/or binding, and the different strength of drug-protein interactions when changing the solution conditions. For this reason, thermodynamic quantities such as Gibbs energies, DeltaG, and entropies of unfolding, DeltaS(m), increase as the solution pH increases provided that additional solvent-exposed hydrophobic residues are present, which were previously buried at room temperature. Moreover, the larger binding affinity at pH 9.0 due to enhanced electrostatic interactions between protein and drug molecules (drug and protein differ in their net electrical charge) additionally collaborates to this residue exposition to solvent as a consequence of the alteration of protein conformation as due to drug binding. Comparison of thermodynamic data between promazine and triflupromazine hydrochlorides also shows that drug-protein affinity and hydrophobicity also affect the thermodynamic denaturation parameters.     

Dissolution behaviour of model alkali-soluble emulsion polymers: effects of molecular weights and ionic strength

The dissolution behaviour of model alkali-soluble polymer emulsions with different molecular weights was studied using conductometric and potentiometric titration and laser light scattering techniques. The behaviour of the copolymer was studied as a function of the degree of neutralisation, α = [NaOH]/[COOH]. The polymer latex swells with increasing α values up to α = 0.5–0.7, after which the dissociation of polymer chains commences. At α = 1.0, all the polymer latexes dissociate into individual polymer chains. By combining the results of static and dynamic laser light scattering, we observed that the polymers have a compact conformation at α = 0. This compact conformation changes to a random coil at around α = 0.5, which then becomes a fully extended coiled conformation at α = 1.0, when all the COOH polymer groups are hydrolysed. The dissolution of low-molecular-weight polymers is faster than that of high-molecular-weight polymers. Received: 15 February 1999 Accepted in revised form: 13 July 1999     

Laser light scattering of the molecular weight distribution of unfractionated phenolphthalein poly(aryl ether sulfone)

Two unfractionated samples of phenolphthalein poly(aryl ether sulfone) (PES-C) were characterized in CHCl₃ at 25°C by applying a recently developed laser light-scattering (LLS) procedure. The Laplace inversion of precisely measured intensity–intensity time correlation function lead us first to an estimate of the characteristic line-width distribution G(Λ) and then to the translational diffusion coefficient distribution G(D). A combination of static and dynamic LLS results enabled us to determine D = (2.69 × 10⁻⁴)M^−0.553, which agrees with the calibration of D = (2.45 × 10⁻⁴)M^−0.55 previously established by a set of narrowly distributed PES-C samples. Using this newly obtained scaling between D and M, we were able to convert G(D) into a differential weight distribution f_w(M) for the two PES-C samples. The weight-average molecular weights calculated from f_w(M) are comparable to that obtained directly from static LLS. Our results showed that using two broadly distributed samples instead of a set of narrowly distributed samples have provided not only similar final results, but also a more practical method for the PES-C characterization. © 1997 John Wiley & Sons, Inc.