Synthesis and characterization of novel zwitterionic lipids with pH-responsive biophysical properties

We report the synthesis and biophysical characterization of a novel class of zwitterionic lipids (ZL) with head groups containing a 3° or 4° amine and carboxylate. ZL form stable liposomes that exhibit head group dependent, pH-responsive biophysical characteristics. These lipids may be suitable components for drug delivery applications due to their ease of synthesis and unique pH-dependent properties.     

Synthesis and characterization of photoswitchable lipids containing hemithioindigo chromophores

The synthesis of four lipids containing the hemithioindigo chromophore as part of the fatty acid is described. Heck reaction of bromophenyl thioacetate esters with acrylonitrile, followed by reduction, ester hydrolysis, and Friedel--Craft acylation--cyclization gave a substituted thioindoxyl that condensed with an alkoxy benzaldehyde to produce the hemithioindigo. "Solventless" nitrile hydrolysis followed by mixed anhydride coupling of the acid with glycerophosphocholine produced lipids bearing two hemithioindigo chromophores. The photochemistry of various hemithioindigo derivatives was studied to confirm the expected photoisomerization in both homogeneous organic solution, and in vesicle bilayer membranes. Characteristic changes in the UV--visible spectra are consistent with fully reversible Z--E photoisomerization. Chromatographic separation of the Z and E isomers of a compound containing a single hemithioindigo chromophore confirmed the spectroscopic analysis and provided a quantitative analysis of the compositions of Z--E isomer mixtures.     

Synthesis of novel cationic lipids for preparation of liposomes to be used in gene therapy of glioma

The synthesis of a series of cationic lipids for the preparation of liposomes to be used in gene therapy is described. The synthetic strategy is designed in few steps and affords good yields. To cite this article: A. Bianco et al., C. R. Chimie 6 (2003).     

Physicochemical and biological characterization of ceramide-containing liposomes: paving the way to ceramide therapeutic application

Ceramides mediate antiproliferative responses, and it has been proposed that increasing the level of ceramides in cancer cells may have a therapeutic antitumor effect. However, ceramides, because of their high "packing parameter" (PP), do not form lipid assemblies that can be dispersed in a form suitable for intravenous administration. We found that nanoliposomes containing short- or medium-chain ceramides are unstable because of their very high (>1.3) PP. To overcome this major obstacle, we included the lipopolymer 2kPEG-DSPE, which reduces the additive PP. The presence of PEG-DSPE allows the formation of highly stable (>1 year) ceramide (Cer)-containing nanoliposomes suitable for systemic administration. Using tumor cell lines, we found that the ceramide cytotoxicity was not impaired by their inclusion in nanoliposomes. The use of 14C-labeled ceramides shows that the C6Cer, but not C16Cer, was transferred from the nanoliposomes to the cells and metabolized efficiently. The difference between the two ceramides is related to the large difference between their critical aggregation concentration and was correlated with the much higher cytotoxity of liposomal C6Cer. The activity of 2kPEG-DSPE as a steric stabilizer (as previously shown for Doxil) was also confirmed for C6Cer-containing nanoliposomes. The 2kPEG-DSPE lipopolymer significantly reduced the desorption rate of the ceramide from the liposome bilayer, thereby allowing liposomes containing C6Cer to reach the tumor site and to demonstrate therapeutic efficacy.     

Dynamics of liposomes constructed from phytanyl lipids

Liposomes constructed from phytanyl lipids3-F/3-NF exhibit very facile transbilayer (“flip-flop”) lipid migration.     

Polymerization of liposomes composed of diene-containing lipids by radical initiators. II. Polymerization of monodiene-type lipids as liposomes

1-Palmitoyl-2(2,4-octadecadienoyl)-sn-glycero-3-phosphocholine (POPC), a polymerizable lipid that contains one diene group in only a 2-acyl chain, was polymerized as liposome in an aqueous medium. Polymerization was initiated by water-insoluble azobisisobutyronitrile (AIBN), or water-soluble azobis(2-amidinopropane) dihydrochloride (AAPD). AIBN was mixed with monomeric lipids, and the mixture was dispersed in an aqueous medium by sonication to prepare AIBN-containing monomeric lipid liposomes. On the other hand, AAPD was simply added to the liposome suspension. The POPC liposomes were easily polymerized by the addition of AAPD, a water-soluble radical initiator, but few were polymerized by AIBN. The results suggested that the diene group in the 2-acyl chain was in an aqueous phase and, therefore, easily polymerized by a water-soluble radical initiator. The polymerized POPC liposomes were revealed to be more stable than those of monomeric ones because the scattered-light intensity from the polymerized POPC liposome suspension changed a little by the addition of Triton X-100. For only the polymerized ones, the liposome structure was confirmed by TEM after addition of an excess amount of Triton X-100.     

Cationic and temperature-sensitive liposomes loaded with eugenol for the application to silk

Silk has been widely used in the clothing industry due to their soft and smooth features, good biocompatibility, good heat dissipation, warmth and ultraviolet resistance. The application of fragrance to silk can significantly improve the performance of silk. However, there are two key scientific problems that need to be solved: slowing down the release rate of fragrances and increasing the scent lasting time of silk. In this study, cationic and temperature-sensitive liposomes were designed and prepared to encapsulate eugenol. These fragrance-loaded liposomes significantly slowed down the release rate of the fragrance and controlled the release rate of the fragrance in a thermo-sensitive manner. The liposomes adhered to the silk through electrostatic adsorption interaction. The positive charge on the fragrance-loaded liposomes neutralized much negative charge on silk and thereby increasing the adhesion efficiency.     

Cationic and temperature-sensitive liposomes loaded with eugenol for the application to silk

Silk has been widely used in the clothing industry due to their soft and smooth features, good biocompatibility, good heat dissipation, warmth and ultraviolet resistance. The application of fragrance to silk can significantly improve the performance of silk. However, there are two key scientific problems that need to be solved: slowing down the release rate of fragrances and increasing the scent lasting time of silk. In this study, cationic and temperature-sensitive liposomes were designed and prepared to encapsulate eugenol. These fragrance-loaded liposomes significantly slowed down the release rate of the fragrance and controlled the release rate of the fragrance in a thermo-sensitive manner. The liposomes adhered to the silk through electrostatic adsorption interaction. The positive charge on the fragrance-loaded liposomes neutralized much negative charge on silk and thereby increasing the adhesion efficiency.     

Preparation and characterization of complexes of liposomes with gold nanoparticles

Gold nanoparticles (Au NPs), which are extremely useful materials for imaging and photothermal therapy, typically require a drug delivery system to transport them to the affected tissue and into the cells. Since liposomes are approved as drug carriers, complexes of liposomes with Au NPs were considered ideal solutions to deliver Au NPs to the target site in vivo. In this study, we prepared complexes of various liposomes with Au NPs via physical absorption and characterized them. The time dependency of the surface plasmon resonance of this complex, which is a unique property of Au NPs, shows that the liposomes promote the formation of stable dispersions of Au NPs under isotonic conditions, even though intact Au NPs aggregate immediately. From a release assay of calcein from liposomes and transmission electron microscopy analysis, the Au NPs were complexed with liposomes without membrane disruption. These complexes could be formed by using cationic liposomes and polyethylene glycol-modified liposomes, as well as by using phosphatidylcholine liposomes, which are useful for drug and gene delivery. We proposed this kind of complex as a nanomedicine with diagnostic and therapeutic ability.     

Synthesis and characterization of pentaerythritol-derived oligoglycol and their application to catalytic Wittig-type reactions

Several pentaerythritol-derived oligoglycols 1 with free hydroxyl groups are readily prepared by a convergent approach. Quantitative (13)C NMR proves to be an efficient tool for the characterization of oligoglycols. The corresponding telluride of oligoglycol 17 is synthesized and used as a good catalyst for Wittig-type reactions in preparing both disubstituted and trisubstituted olefins in good to high yields.     

Electroformation of giant liposomes from spin-coated films of lipids

This paper describes spin-coating of solutions of lipids and using the resulting thin films for electroformation of giant liposomes. Spin-coating made it possible to generate uniform films of lipids with controllable thickness over large surfaces (>25 cm(2)) of indium tin oxide. Establishing a range of thicknesses optimal for electroformation (25-50 nm), we demonstrate formation of giant liposomes from lipids (such as asolectin, phosphatidylserine, and phosphatidylglycerol) that do not readily form giant liposomes from traditional, droplet-derived films. We compared liposomes from a spin-coated film of lipids to liposomes formed from traditional droplet-derived films and found that spin-coated films produced larger (by factor of 2-5) and more abundant liposomes than droplet-derived films of lipids. Electroformation from spin-coated, homogenous lipid films of optimal thickness provided a reproducible way to obtain liposomes with diameters that are predominantly larger than 30 microm over the entire surface of formation.     

Synthesis,characterization, and application of helical polymers

This review mainly describes the asymmetric synthesis of optically active polymers with helical conformation. Bulky methacrylates such as triphenylmethyl methacrylate and 1-phenyldibenzosuberyl methacrylate give one-handed helical and optically active polymers with almost perfectly isotactic main chain conformation by polymerization with chiral anionic initiators. The radical polymerization and copolymerization of these monomers under chiral conditions also afford optically active polymers with prevailing one-handed helicity. N, N-Disubstituted acrylamides also give optically active, helical polymers in the asymmetric anionic polymerization. Optically active polyisocyanates with a prevailing one-handed helical structure have been prepared in the copolymerization of an achiral isocyanate with a small amount of an optically active isocyanate and also in the polymerization of alkyl and aromatic isocyanates with optically active lithium alkoxide or amide compounds. The existence of a stable helical structure for polychloral has been successfully proved with the helical oligomers of chloral. One-handed helical polyisocyanides have been prepared by helix-sense-selective polymerization of bulky isocyanides and also by the cyclopolymerization of a 1, 2-diisocyanobenzene derivative with the Pd complex of a one-handed helical oligomer.     

Synthesis and characterization of phosphorous-bridged bisphenoxy titanium complexes and their application to ethylene polymerization

Phosphorous-bridged bisphenoxy titanium complexes were synthesized and their ethylene polymerization behavior was investigated. Bis[3-tert-butyl-5-methyl-2-phenoxy](phenyl)phosphine tetrahydrofuran titanium dichloride (4a) was obtained by treatment of 3 equiv of n-BuLi with bis[3-tert-butyl-2-hydroxy-5-methylphenyl](phenyl)phosphine hydrochloride salt (3a) followed by TiCl₄(THF)₂ in THF. THF-free complexes 5a-5d were synthesized more conveniently by the direct reaction of MOM-protected ligands (2a-2d) with TiCl₄ in toluene. X-ray analysis of 4a revealed that the ligand is bonded to the octahedral titanium (IV) center in a facial fashion and two chlorine atoms possess cis-geometry. Complexes 4a and 5a-5d were utilized as catalyst precursors for ethylene polymerization. Complex 5c gave high molecular weight polyethylene (M_w = 1,170,000, M_w/M_n = 2.0) upon activation with Al(ⁱBu)₃/[Ph₃C][B(C₆F₅)₄] (TB). Ethylene polymerization activity of 5d activated with Al(ⁱBu)₃/TB reached 49.0 × 10⁶ g mol (cat) ⁻¹ h⁻¹.     

Synthesis and characterization of lanthanum chloranilate complex: application to spectrophotometric determination of anions

Lanthanum chloranilate complex has been synthesized and characterized using different techniques like Infrared spectroscopy and CHN analysis. It has been used for the development of spectrophotometric method of determination of anions like fluoride, EDTA and iodate. The determination is based on the reaction of these anions with the lanthanum ion in the chloranilate complex resulting in the liberation of an equivalent amount of chloranilate anion, the colour of which was measured. The experimental conditions, which affect the optical density, are studied to get maximum sensitivity. Interference studies were carried out with various ions. The method has been applied to the determination of these ions in actual samples viz. EDTA in detergents and iodate in salt.     

Synthesis of metal-chelating lipids to sensitize lanthanide ions

Sensitization of lanthanide ions is important for lanthanide ion-based assays and sensing. To the best of our knowledge, there are very few reports of lanthanide ion sensitization after it is incorporated into the liposome surface. This paper describes the syntheses of several saturated and polymerizable metal-chelating lipids based on chelidamic acid. The lipids are synthesized either from (S)-ornithine or racemic 2,3-diaminopropanoic acid. These lipids as well as polymerized liposomes incorporating these lipids sensitize lanthanide ions. Liposomes from the lipid 18-Eu(3+) provided a probe that relies not only on the emission wavelengths of Eu(3+) but also on a reproducible lifetime that can be used for protein identification.     

二茂铁柠檬酰腙缩聚物的合成、表征及应用

通过1,1’-二乙酰基二茂铁与柠檬酸三甲酰肼缩合,制成了二茂铁柠檬酰腙聚合物(Fc-NM),再在DMF中与金属(M=Cu、Co、Ni、Mn、Zn)醋酸盐配位,制成五种二茂铁酒石酰腙金属配位聚合物(Fc-NM-M)。用IR、TGA、XRD、SEM及介电常数进行表征,结果表明,在适于移动通信应用的0.2-2.0GHz频段,Fc-NM有较高的介电常数(ε‘),较低的介电损耗(ε″),将其制成倒F型微带天线有良好的缩波性能,方向图及较高的增益。因此Fc-NM作为一种天线新材料,可用于小型化、多功能化及高增益的双频微带天线。     

Synthesis,characterization and application of soluble fullerenated polymer materials

This article only deals with the topic of intense interest to us and to a considerable extent of our own experimental results on the synthesis,characterization and application of C60-con-taining functional polymers such as poly(N-vinylcarbazole),polystyrene and polyacrylonitrile-based fullerene polymers.The results demonstrate that [60] fullerene can be directly incorporated into a variety of functional polymers by copolymer-ization or grafting,but also can be used to modify or improve the electronic,optical and physicochemical properties of polymers.Both the stereo-electroniceffect and the steric hindrance of C60 have an important influence on the structure and physicochemical properties of the parent polymer.     

Synthesis, characterization and sensing application of novel semiconductor oxides

Mesoporous SnO(2) with high surface areas were synthesized using a cationic surfactant (N-cetyl-N,N,N-trimethylammonium bromide) as a synthetic template. Acidity of the starting synthesis slurry was used as one of the controlling parameters for the synthesis. After the SnO(2) was synthesized at pH 7.15, it was calcined at 723 K for 10 h in air. It had a BET surface area of 156.8 m(2) g(-1) with a pore diameter of 38.4 A. Infrared spectroscopy (FTIR) and thermal analysis techniques (thermogravimetry and differential thermal analysis) showed that the surfactant was incorporated in the mesopores of SnO(2) and calcination in air at 673-723 K was needed to remove the surfactant completely from the mesopores. The effects of SnO(2) surface area on its gas sensing properties were also investigated. It was observed that SnO(2) with higher surface areas had much higher sensitivities to hydrogen at 573 K.