Reduced fluidity of dipalmitoyl phosphatidic acid membranes by salicylic acid

This paper presents DSC and NMR study of how the kerotolytic drug, salicylic acid (SA), affects the thermotropic and morphological behavior of a model membrane, dipalmitoyl phosphatidic acid (DPPA). The membrane-drug system has been studied in the multilamellar vesicular (MLV) and in the unilamellar vesicular (ULV) forms, for SA/DPPA molar ratios from 0 to 0.5. The mode of interaction of SA molecules with DPPA is similar in MLV and ULV. Chain-melting transition becomes sharper and shifts to higher temperatures in the presence of the drug, implying an enhanced co-operativity of the acyl chains. NMR and DSC data indicate that the drug molecules are located in the aqueous interfacial region neighboring the lipid headgroups. The membrane becomes more rigid in the presence of the drug molecules, due to a stronger interaction between the lipid headgroups leading to reduced permeability. ULVs are destroyed by even a short equilibration at room temperature, whereas prolonged equilibration of the MLV only leads to a slightly reduced interaction between the lipid headgroups due to sequestering of the drug molecules in the interfacial aqueous region.     

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     

Reversible size of shear-induced multi-lamellar vesicles

We have investigated the reversibility in the shear-induced multi-lamellar vesicle (MLV) size during stepwise cycling of the shear rate by employing common rheometry, polarized light microscopy and rheo-optic techniques. We thus address the question whether there is a true MLV steady state, irrespective of history. The system studied, was the nonionic surfactant triethylene glycol decyl ether (C₁₀E₃) with a concentration of 40 wt.% in D₂O and a constant temperature of 25°C. It was found that the MLV size varies reversibly with varying shear rate, and hence there exists a true steady state in the presence of shear flow. The experimental observations of reversibility are however restricted to higher shear rates. Because the transformation of the size results from the shear strain, the process is very slow at lower shear rates, where the steady state cannot be reached within a reasonable experimental time.     

高效液相色谱-荧光检测法测定敬钊毒素-I的磷脂膜结合活性

敬钊毒素-I(JZTX-I)是一种能够抑制心肌钠通道失活的新型蜘蛛神经毒素,该文结合高效液相色谱与色氨酸荧光测定技术研究了JZTX-I的磷脂膜结合活性。脂质体共沉淀实验表明,JZTX-I具有不依赖于带负电荷磷脂组成的生物膜结合活性。当加入由酸性或中性磷脂构成的脂质体后,JZTX-I能够分别产生6.4和4.7 nm的蓝移以及7.4和8.0 nm的红移激发漂移,显示JZTX-I能够插入磷脂膜,同时该分子疏水表面的色氨酸残基处于一个运动受限的界面区域。荧光淬灭实验进一步证实,与脂质体结合能够减少该毒素分子表面色氨酸残基的溶剂暴露。该研究结果为阐明JZTX-I的离子通道门控调节机制提供了新的信息。     

Interactions of dicarboxylic porphyrins with membranes in relation to their ionization state

The interactions of dicarboxylic porphyrins with membrane systems are discussed with particular emphasis on the effect of the charge of the porphyrin and the nature of the side-chains. The incorporation of hematoporphyrin or related dicarboxylic porphyrins within small unilamellar vesicles as membrane models is favored by a decrease of the pH in the range of physiological pH values. This effect might play an important role in the retention of porphyrins by tumors, which are more acidic than normal tissues. Kinetics studies also show that the partition of the porphyrin between the lipidic bilayer and the aqueous phase is governed by its release rate rather than by its incorporation rate.     

Al3+离子对卵磷脂聚集体结构的影响

本文用浊度滴定(UV-Vis)、透射电镜(TEM)和激光光散射(QELS)等方法对Al³⁺离子与卵磷脂(EYPC)囊泡之间的相互作用及其这种相互作用对溶液中磷脂微结构的影响进行了研究。结果表明，一定量的Al³⁺离子使EYPC多层囊泡转变为线团状聚集体;Al³⁺与牛磺胆酸钠(TC)的协同作用可以破坏EYPC的多层囊泡结构，促进相转变，形成混合胶束。     

Solvent replacement to thermo‐responsive nanoparticles from long‐subchain hyperbranched PSt grafted with PNIPAM for encapsulation

Long‐subchain hyperbranched polystyrene (lsc‐hp PSt) with uniform subchain length was obtained through copper‐catalyzed azide‐alkyne cycloaddition click chemistry from seesaw macromonomer of PSt having one alkynyl group anchored at the chain centre and two azido group attached to both chain ends [alkynyl‐(PSt‐N₃)₂]. After precipitation fraction, different portions of lsc‐hp PSt having narrow overall molecular weight distribution were obtained for further grafting with alkynyl‐capped poly(N‐isopropylacrylamide) (alkynyl‐PNIPAM), which was obtained via single‐electron transfer living radical polymerization of NIPAM with propargyl 2‐bromoisobutyrate as the initiator and grafted onto the peripheral azido groups of lsc‐hp PSt via click chemistry. Thus, amphiphilic lsc‐hp PSt grafted with PNIPAM chains (lsc‐hp PSt‐g‐PNIPAM) was obtained and would have star‐like conformation in tetrahydrofuran (THF). By replacing THF with water, lsc‐hp PSt‐g‐PNIPAM was dissolved at molecular level in aqueous solution due to the hydrophilicity of PNIPAM and exhibited thermal induced shrinkage of PNIPAM arms. The water‐insoluble lsc‐hp PSt would collapse densely and could be served as a reservoir to absorb hydrophobic chemicals in aqueous solution. The influence of overall molecular weight of lsc‐hp PSt on the absorption of pyrene was studied. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Nanoreactors for Chemical Synthesis and Biomedical Applications

With the rapid development of nanoscience and nanotechnology, various types of functional nanoreactors have been designed for diverse applications. Here, the recent evolution of the rational design of nanoreactors for chemical synthesis and biomedical applications are briefly summarized and discussed. The presence of nanoreactors provides constrained space isolated from the surrounding environment. Scientists are committed to studying changes in chemical reactions when the reaction system is confined to the nanosized space. Nanoreactors accelerate the reaction rate and even change mechanism of some chemical reactions. Cells and organelles as natural nanoreactors are also discussed. The development of intracellular synthesis makes it possible to realize various applications in biomedicine. The challenges on the rational design of nanoreactors and perspectives are also discussed.     

Thermoresponsive polymersome from a double hydrophilic block copolymer

The article describes synthesis and thermally triggered self‐assembly of a Poly (ethylene oxide)‐block‐poly (N‐insopropylacrylamide) (PEO‐b‐PNIPAm) in aqueous medium. At rt, the polymer remains as unimer, however, at lower critical solution temperature (LCST) of PNIPAm (32 °C), it forms a rather large undefined aggregate which at slightly elevated temperature (～40 °C) converges to well defined polymersome structure (Critical aggregation concentration = 0.45 mg/mL) with hydrodynamic diameter of 40–50 nm. By lowering the temperature, initial swelling of the compact vesicle followed by reversible disassembly to unimer was noticed. The polymersome exhibits encapsulation ability to a hydrophilic dye Calcein which can be spontaneously released by lowering the temperature below cloud point. Likewise a hydrophobic dye namely 8‐Anilino‐1‐naphthalenesulfonic acid (ANS) can also be encapsulated and released by thermal trigger. Detail photoluminescence studies reveal ANS dye can be used as a generalized probe molecule for detecting LCST of a thermoresponsive polymer by “fluorescence on” above LCST even by cursory observation. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2444–2451