Micro construction of poly(epsilon-caprolactone)/poly(L-lactic acid) blend film by solution casting under microwave irradiation

The micro construction of poly(epsilon-caprolactone) (PCL) and poly(L-lactic acid) (PLLA) blend films fabricated by solution casting under microwave irradiation was investigated by selective enzymatic degradation and scanning electron microscopy (SEM). The results were totally different from the blends obtained by conventional methods. The blend was more homogeneous and the PCL continuous phase more compact as no spherulites and tiny zone separation were observed from the film surface and no PCL network was observed inside the film, and the degradation of a PCL plank by Pseudomonas lipase was significantly retarded. The distributed PLLA micro spheres were enlarged and amorphous. The thermal behavior of the blend by microwave heating revealed that PCL and PLLA underwent a melting process, which induced the variations of the PCL phase and PLLA spheres. The weight loss caused by degradation of the PCL/PLLA blend obtained by conventional methods (B50c) is greater than that of the blend obtained by microwave methods (B50m), which reflects the change in morphology from a loose PCL network (B50c) to a dense PCL plank (B50m).     

Enzymatic hydrolysis reaction of phospholipids in monolayers

The hydrolysis reaction of , and , -dipalmitoylphosphatidylcholine (DPPC) catalized by bee venom phospholipase A₂ was studied in spreading monolayer at the water/air interface. DPPC and the hydrolysis products, palmitic acid and -lysophosphatidylcholine, palmitoyl were characterized at the interface by means of surface pressure, surface potential and ellipsometric measurements. Furthermore, mixed monolayers of reagents and products were investigated to ascertain their miscibility. The results show that the hydrolysis reaction can be followed by the decrease of surface pressure with time on subphases containing β-cyclodextrin, a well-known complexing agent of many amphiphilic compounds. The order of the reaction, the kinetic constant and other kinetic parameters are deduced.     

Temperature-sensitive luminescence of tris (β-diketone) europium chelates for monitoring high-speed cationic photopolymerizations

The temperature-dependent luminescence of tris (β-diketone) chelates of europium was used for in situ temperature measurements during cationic photopolymerizations of vinyl ethers. These molecular-level luminescent probes provided a real-time, noninvasive method for monitoring temperature during these high-speed polymerizations. Two specific probes, tris (benzoyl-1, 1, 1-trifluoroacetone) europium and tris (1,1,1,5,5,5,-hexafluoroacetylacetone) europium, met several stringent spectral and performance requirements for application in our system. The luminescence from these probes exhibits a reproducible temperature dependence over a wide temperature range and is not sensitive to changes in viscosity. In situ temperature profiles obtained using this novel technique verified the importance of thermal effects during these highly exothermic photopolymerizations. These studies have demonstrated the utility of the tris(β-diketone) europium chelates for characterizing the temperature during high-speed photopolymerizations that cannot be monitored using conventional techniques. © 1995 John Wiley & Sons, Inc.     

The regioselectivity of the formation of 2-pyrazolylthiazoles and their precursors from the reaction of 2-hydrazinothiazoles with 4,4,4-trifluoro-1-hetaryl-1,3-butanediones

Reaction of 2-hydrazinothiazoles 1 with 1-thienyl- and 1-furyl-1,3-butanediones 2a,b in methanol in the presence of hydrochloric acid mainly leads to a mixture of pyrazoles 3 and pyrazolines 4 or pyrazoles 3 and 5 in strong acidic conditions. Isomeric hydrazones 6 and pyrazolines 4 were formed and isolated in these reactions in the absence of hydrochloric acid. It has been shown that the regioselectivity in the reaction of diketones 2 with hydrazine 1 is governed by both the concentration of acid and the nature of substituents in the 1,3-diketones 2. Cyclization of hydrazones 6 is shown to occur under milder conditions than dehydration for pyrazolines 4. The new heterocyclic compounds were prepared and fully characterized by NMR spectra and by X-ray analysis for 3c.     

First synthesis of α-aminophosphonates from natural porphyrin derivatives by the Kabachnik—Fields reaction

A preparative procedure is proposed for the synthesis of α-aminophosphonates of natural porphyrins by the microwave-assisted Kabachnik—Fields reaction.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 256–259, January, 2005.     

The Role of Carnitine Acyltransferases in the Maintenance of Cell Function

Summary. Carnitine acyltransferases catalyse equilibria between acyl-CoA esters and the respective acylcarnitines. Therefore, they act not only as pathway enzymes, but also as modulators of acyl-CoA concentrations within individual sub-cellular compartments. Because acyl-CoA esters are potent biologically active metabolites, carnitine acyltransferase activities are potentially able to affect a diverse range of physiological processes, ranging from insulin secretion, to appetite control, and insulin sensitivity of tissues. The distinctive subcellular distributions of the different types of carnitine acyltransferases also enables them to participate in the transfer of acyl moieties across intracellular membranes, and of particular acylcarnitine esters across the plasma membrane and into the plasma. Pharmacological strategies that make use of these properties to improve cell function are discussed.     

Dynamical tunneling through a chaotic region

It is shown that a non-vibrating diatomic molecule (i.e. a rigid rotor) in the presence of a strong laser field changes its hindered rotational motion (which on the average is in resonance with the oscillating time dependent field) from anti-clockwise to clockwise (hindered) rotational motion. This transition is classically forbidden and is another example of a quantum mechanical tunneling phenomenon occurring due to the time-reversal symmetry of the Hamiltonian. Classically, the two stable rotational modes are separated by an extended chaotic region in phase space. The Husimi representation of the quasienergy states of the time-periodic quantum system enables us to localize wave packets inside the classical stability islands. The effect of the field and the molecular parameters on the perioid of this oscillation is obtained from the quasienergy splittings without the need to carry out long time dependent computations. An analytical analysis of the dynamical tunneling using an extended version of the (t,t) formalism recently developed (J. Chem. Phys.99, 4590 (1993)) is in remarkable agreement with the numerical results.Member of the Minerva center of non-linear physics of complex systems at the Technion     

An unexpected allomer of chlorophyll: 13(S)-hydroxy-10-methoxychlorophyll b

The allomerization of chlorophyll b in methanol produced 13²(S)-hydroxy-10-methoxychlorophyll b in a yield of ca. 8%. The formation of this allomer was totally unexpected, as 10-substituted chlorophylls have never been reported before. The structure of the new chlorophyll b derivative was determined on the basis of UV/Vis, FAB-MS, ¹H NMR and 2D ROESY NMR spectra. This letter focuses on the NMR analysis.     

A further breakthrough in biphasic, rhodium-catalyzed hydroformylation: the use of Per(2,6-di-O-methyl)-β-cyclodextrin as inverse phase transfer catalyst

Solvent free biphasic hydroformylalion of various water-insoluble terminal olefins can be achieved in high yields and sclcctivitics by using a water-soluble rhodium/triphenylphosphine trisulfonate catalyst and per(2,6-di-o-mclhyl)-β-cyclodcxtrin as inverse phase transfer catalyst. The catalytic activities were up to ten times higher than those observed without pcr(2,6-di-o-methyl)-β-cyclodextrin.     

Applicability of polymer theories to the thermodynamics of proteins at the air/water interface: example of β-lactoglobulin

Knowledge of the equation of state of adsorbed or deposited layers of proteins at the air/water interface is of fundamental interest in the understanding of the surface activity of these molecules. Using scaling laws of current polymer theories, it has been shown that the equation of state of the interfacial layer in the semi-dilute regime should relate the surface pressure to the surface concentration through a power law. The exponent of this power law should reflect the quality of the solvent and the conformation of the adsorbed polypeptide chain. In the case of β-lactoglobulin layers, in the range of surface concentrations that should correspond to the semi-dilute regime, the relationship between surface pressure and surface concentration is expressed as a power law. The exponent of this power law is strongly influenced by the nature of the aqueous substrate and by the net charge of the protein molecule. The use of scaling laws gives a coherent view of the expansion of the polypeptide chain in the interfacial layer and of the relationship between surface concentration and surface pressure in the semi-dilute regime. This result favours a strong similarity between β-lactoglobulin and a polymer chain in the interfacial layer. It is concluded that current theories of polymer adsorption could be applied to interfacial protein layers.