Product-retardation and -activation of catalytic hydrolysis by phospholipase D in small unilamellar vesicles of egg yolk phosphatidylcholine

 We evaluated the hydrolysis of egg yolk phosphatidylcholine (PC) by phospholipase D from Streptomyces chromofuscus (PLD) in small unilamellar vesicles (SUV) in presence of 50 μM Ca²⁺. After initial choline production (hydrolysis of 1.5% of the PC at the outer leaflets of the vesicle bilayers), the hydrolysis was reduced to 5% of the initial velocity. The kinetic behavior in SUV of premixed PC and a low percentage of the hydrolysis product, phosphatidic acid (PA), was similar to that of PC SUV. The reduced velocity disappeared when the membrane structure was disintegrated by means of a nonionic surfactant. In the retardation phase, the partially hydrolyzed vesicles (postsubstrates) had much higher affinity for PLD than fresh PC SUV. These results indicated that small clusters of the product, PA, at the vesicle surface were responsible for the reduced velocity of hydrolysis. The initial velocity increased in a biphasic manner with the substrate concentration. At a PC concentration range up to 4 mM, the experimental data fit Michaelis–Menten kinetics. At concentrations above 6 mM, the velocity again markedly increased. Negatively charged mixed vesicles of PC and PA did not have such kinetics. Furthermore, adding PC SUV to the postsubstrates, where the fraction of free PLD was less than 0.05, induced steep choline production. These results showed that PLD bound to vesicles had higher activity than free PLD. We speculated that PLD bound to vesicles collided with and was directly transferred to PC SUV when the fraction of free PLD in aqueous medium was very small. Received: 5 November 1996 Accepted: 26 February 1997     

Controlled preparation of aluminum borate powders for the development of defect-related phosphors for warm white LED lighting

The optimization of the elaboration conditions of a new family of highly emissive white phosphors based on glassy yttrium aluminum borates (g-YAB) compositions is presented. Their preparation from solutions is based on the polymeric precursor method (modified Pechini process), involving non-toxic and low cost precursors. The resulting resins were first dried at moderate temperatures followed by two-step annealing treatments of the obtain powders under controlled atmospheres: a first pyrolysis under nitrogen followed by a calcination under oxygen. This favored the gradual oxidation of organic moieties coming from starting materials, avoiding uncontrolled self-combustion reactions, which generate localized hot spots. This prevented phase segregations and the formation of pyrolytic carbon or carbonates, which are strongly detrimental to the luminescence properties. Thus, coupled chemical analyses and luminescence characterizations showed the high chemical homogeneity of the resulting powders and their intense emissions in the whole visible range. These emissions can be tuned from blue to warm white by adjusting the calcination temperature that is an important advantage for the development of LED devices. We showed that impurities of monovalent and divalent cations act as quenching emission centers for these phosphors. Therefore, by increasing the purity grade, we significantly enhanced the PL emissions leading to high internal quantum yields (80–90%). Finally, cathodoluminescence emissions showed the homogeneous dispersion of emitting centers in the g-YAB matrix.     

含氨基酸侧链的有机硅高分子催化剂 ⅩⅤ.γ-(L-酪氨酰胺基)丙基硅氧烷钯催化剂的合成加氢活性及其结构表征

本文报导了四种不同N/Pd摩尔比的聚γ-(L-酪氨酰胺基)丙基硅氧烷钯催化剂的合成及其催化加氢活性,这类催化剂与聚γ-((L-酷氨酸)丙基硅氧烷钯催化剂相比较,虽然均具有类似的N→Pd配位的活性中心组成,但它们对底物的加氢活性则明显不同,前者对丙烯腈、丙烯酸、环己烯和1-癸烯的催化活性比后者高,对苯乙烯则相反。N/Pd摩尔比、反应温度、溶剂以及体系的pH值对催化活性的影响,两者的情况大致相同,标题催化剂对衣康酸的催化加氢,产物的光学纯度为30％。     

聚合物介质中盐离解行为的温度依赖性研究

<正> 近十年来尽管聚合物-盐复合物作为潜在的理想电解质材料已得到广泛研究,人们对于在象聚合物这样的高粘度介质中盐的离解行为仍缺乏了解。特别是关于盐离解度的温度依赖性,不同的作者对相似的体系曾得出截然相反的结论。最近,Angell和许康等相继通过不同研究途径证实了在上述介质中盐离解产生的自由离子数n随温度上升而下降,其趋势可由Arrhenius公式表示:     

Assessment of the In Vivo Release and Biocompatibility of Novel Vesicles Containing Zinc in Rats

This paper is focused on the in vivo release and biocompatibility evaluation in rats of some novel systems entrapping zinc chloride in lipid vesicles. The particles were prepared by zinc chloride immobilization inside lipid vesicles made using phosphatidylcholine, stabilized with 0.5% chitosan solution, and dialyzed for 10 h to achieve a neutral pH. The submicrometric systems were physico-chemically characterized. White Wistar rats, assigned into four groups of six animals each, were treated orally with a single dose, as follows: Group I (control): deionized water 0.3 mL/100 g body weight; Group II (Zn): 2 mg/kg body weight (kbw) zinc chloride; Group III (LV-Zn): 2 mg/kbw zinc chloride in vesicles; Group IV (LVC-Zn): 2 mg/kbw zinc chloride in vesicles stabilized with chitosan. Haematological, biochemical, and immune parameters were assessed after 24 h and 7 days, and then liver fragments were collected for histopathological examination. The use of zinc submicrometric particles—especially those stabilized with chitosan—showed a delayed zinc release in rats. No substantial changes to blood parameters, plasma biochemical tests, serum complement activity, or peripheral neutrophils phagocytic capacity were noted; moreover, the tested substances did not induce liver architectural disturbances. The obtained systems provided a delayed release of zinc, and showed good biocompatibility in rats.     

One-pot synthesis of PDMAEMA nanocapsules for controlled release of hydrophobic cargo

In this work, poly((N,N-dimethyl amino)ethyl methacrylate) (PDMAEMA) homopolymers are synthesized using RAFT technique, which is then used as stabilizers to prepare miniemulsion droplets in a toluene/hexadecane(HD)/1,2-Bis-(2-iodoethyl)ethane(BIEE)/hydrophobic molecule/water mixture. Upon the reaction between BIEE and the stabilizers of miniemulsion droplets, the polymeric nanocapsules are formed and capable of encapsulating hydrophobic molecule in their oil core in one-step reaction. The release of hydrophobic cargo from the nanocapsules can be controlled by the variation of amount of surfactant (Tween®20) in the release medium and a long duration sustained release was achieved.     

Development and Optimization of an Ion‐selective Electrode for Serotonin Detection

Our studies are focused on the development of novel potentiometric sensors for the quantification of the neurotransmitter serotonin. Therefore, ion‐selective electrodes based on plasticized PVC membranes are applied. The electroactive part of the membrane consists of an ion pair complex formed between the protonated analyte and a carborane anion [Co(1,2‐C₂B₉H₁₁)₂]⁻. The analytical performance of the electrode was studied regarding sensitivity, concentration range, limit of detection and potential stability. The ion‐selective electrodes were optimized with respect to the material of the transducing element, as well as the membrane thickness and its composition. Stable, all solid state ISEs could be developed, using the non‐polar plasticizer NPOE and a graphite rod with high surface area as transducing element. We thus achieved a near Nernstian response over three decades of concentration (2.25⋅10^‐5‐1.00⋅10^‐2 M) and a limit of detection in the μ‐molar range for the optimized electrodes. The electrodes could successfully be miniaturized using carbon based screen printed electrodes.     

LHRH/TAT dual peptides-conjugated polymeric vesicles for PTT enhanced chemotherapy to overcome hepatocellular carcinoma

Combination therapy such as photothermal therapy (PTT) enhanced chemotherapy is regarded as a promising strategy for cancer treatment. Herein, we developed redox-responsive polymeric vesicles based on the amphiphilic triblock copolymer PCL-ss-PEG-ss-PCL. To avoid the limited therapeutic effect of chemotherapeutic drugs caused by systemic exposures and drug resistance, the redox-sensitive polymeric vesicles were cargoed with two chemotherapeutics: doxorubicin (DOX) and paclitaxel (PTX). Besides, indocyanine green (ICG) was encapsulated, and cell-penetrating peptides and LHRH targeting molecule were modified on the surface of polymeric vesicles. The results indicated that the polymeric vesicles can load different kinds of drugs with high drug loading content, trigger drug release in responsive to the reductive environment, realize high cellular uptake via dual peptides and laser irradiation, and achieve higher cytotoxicity via chemo-photothermal combination therapy. Hence, the redox-responsive LHRH/TAT dual peptides-conjugated PTX/DOX/ICG co-loaded polymeric micelles exhibited great potential in tumor-targeting and chemo-photothermal therapy.     

Micromechanical modeling of the elasto-viscoplastic behavior of semi-crystalline polymers

A micromechanically based constitutive model for the elasto-viscoplastic deformation and texture evolution of semi-crystalline polymers is developed. The model idealizes the microstructure to consist of an aggregate of two-phase layered composite inclusions. A new framework for the composite inclusion model is formulated to facilitate the use of finite deformation elasto-viscoplastic constitutive models for each constituent phase. The crystalline lamellae are modeled as anisotropic elastic with plastic flow occurring via crystallographic slip. The amorphous phase is modeled as isotropic elastic with plastic flow being a rate-dependent process with strain hardening resulting from molecular orientation. The volume-averaged deformation and stress within the inclusions are related to the macroscopic fields by a hybrid interaction model. The uniaxial compression of initially isotropic high density polyethylene (HDPE) is taken as a case study. The ability of the model to capture the elasto-plastic stress-strain behavior of HDPE during monotonic and cyclic loading, the evolution of anisotropy, and the effect of crystallinity on initial modulus, yield stress, post-yield behavior and unloading-reloading cycles are presented.     

Lamellar-to-nematic phase transition in a lipid-surfactant mixture

A lyotropic system, consisting of a lecithin (DMPC) and a non-ionic surfactant (C₁₂E₅) in water was studied. The system exhibits a lamellar-to-nematic phase transition. The nematic phase appears as the temperature is decreased and only exists in a very limited temperature and concentration range, for specific lipid-to-surfactant ratios. While a lamellar phase is found at higher temperatures in both mixed and pure C₁₂E₅ systems, the transition to the nematic phase at lower temperatures coincides with a micellar phase in the pure C₁₂E₅ system. The transition appears to be driven by the strong temperature dependence of the surfactant film spontaneous curvature. The structural properties of the lamellar phase close to the lamellar-to-nematic boundary have been studied by polarised light microscopy and small-angle neutron and X-ray scattering experiments. The signature of a helical defect with Burgers vector of magnitude 2 is apparent in our data, close to the lamellar-to-nematic phase transition. The proliferation of screw dislocations in the lamellar phase might be a plausible mechanism for driving this transition. Received 6 July 1999 and Received in final form 17 April 2000