Fluorescence resonance energy transfer between polydiacetylene vesicles and embedded benzoxazole molecules for pH sensing

A mixed polydiacetylenes (PDAs) vesicle with a phospholipid unit is functionalized by entrapping fluorescent benzoxazole (BZ) molecules inside the PDA vesicles. Upon photo-polymerization and heat-treatment of the self-assembled vesicles, a weak red fluorescence can be observed. Excitation of BZ molecules enables the amplification of PDA vesicle fluorescence resonance energy transfer (FRET) to more than four times that of the direct excitation of red-phase PDA vesicles. The backbone of the PDA vesicles act as energy acceptors, which absorb energy from embedded BZ donor molecules inside the PDA vesicle, which emit blue fluorescence. The amplified red emission from the PDA vesicle can be altered by pH changes in the aqueous solution and thus the PDA vesicle mixed with a phospholipid and entrapped molecules inside can be a promising candidate as a pH sensor.     

Spontaneous vesicle formation from trisiloxane-tailed gemini surfactant

The spontaneous vesicle formation from a novel trisiloxane-tailed gemini surfactant were reported. The surface tension measurements revealed that aggregates are formed, and dynamic light scattering (DLS) measurements suggested the aggregates are vesicles. The size and morphology were observed by transmission electron microscopy (TEM). The vesicle formation was further confirmed by dye entrapment studies.     

Giant Vesicles: Preparations and Applications

There is considerable interest in preparing cell‐sized giant unilamellar vesicles from natural or nonnatural amphiphiles because a giant vesicle membrane resembles the self‐closed lipid matrix of the plasma membrane of all biological cells. Currently, giant vesicles are applied to investigate certain aspects of biomembranes. Examples include lateral lipid heterogeneities, membrane budding and fission, activities of reconstituted membrane proteins, or membrane permeabilization caused by added chemical compounds. One of the challenging applications of giant vesicles include gene expressions inside the vesicles with the ultimate goal of constructing a dynamic artificial cell‐like system that is endowed with all those essential features of living cells that distinguish them from the nonliving form of matter. Although this goal still seems to be far away and currently difficult to reach, it is expected that progress in this and other fields of giant vesicle research strongly depend on whether reliable methods for the reproducible preparation of giant vesicles are available. The key concepts of currently known methods for preparing giant unilamellar vesicles are summarized, and advantages and disadvantages of the main methods are compared and critically discussed.     

Fluorescence of Cascade Blue™ inside nano-sized porous shells of silicate

Cascade Blue™ (CB) dye at a concentration as high as 0.227 M was encapsulated within nano-sized porous silicate shells, and its relative fluorescence yield determined over the pH range of 1.8–12.3, using 380 nm as the excitation wavelength. The results were compared with those obtained in aqueous solution using similar pH and total dye concentration. Near neutral pH, the relative fluorescence yields of CB inside the shells exhibited little fluorescence quenching, even though a high concentration of the dye was trapped inside the particles, while the peak wavelength of fluorescence was shifted from 420 nm in solution to 430 nm in shells. Both in shells and solution, the relative fluorescence intensity decreased as the solution pH was raised from 2 to 4, and in shells it nearly disappeared at about pH 3–4. As the pH was further increased, the red shift of fluorescence peak in the shell-trapped dyes was evident at pH 5 and its fluorescence intensity regained equal to that in acid. In the neutral pH range, the fluorescence intensity of CB in the shells was similar to that of the equivalent total concentration of the CB in solution. In solution, a similar red shift of the fluorescence maximum of CB to 430 nm was observed only above pH 9. These observations suggest that the fluorescence intensities of dyes trapped inside nano-sized porous silicate shells can be equal to or higher than that observed in solution under comparable conditions, leading to several hundreds times more fluorescent intensity when it is measured per single shell rather than per unit fluorophore.     

Gene expression within cell-sized lipid vesicles

Functional protein synthesis was observed in cell-sized lipid vesicles following encapsulation of a gene-expression system. Expression of rsGFP (red-shifted green fluorescent protein) within individual vesicles was observed by fluorescence microscopy. Interestingly, at the early stage of the reaction, the expression efficiency inside the vesicle was remarkably higher than that in the solution outside. The synthesized rsGFP in individual vesicles is safe from attack by proteinase K added to the external aqueous solution. Studies on cell-sized vesicles expressing protein should contribute to a fundamental understanding of certain aspects of living systems and will be useful for practical applications, such as the construction of microreactors.     

Overview of preparation methods of polymeric and lipid-based (niosome,solid lipid,liposome) nanoparticles: A comprehensive review

A wide number of drug nanocarriers have emerged to improve medical therapies, and in particular to achieve controlled delivery of drugs, genes or gene expression-modifying compounds, or vaccine antigens to a specific target site. Of the nanocarriers, lipid-based and polymeric nanoparticles are the most widely used. Lipid-based systems like niosomes and liposomes are non-toxic self-assembly vesicles with an unilamellar or multilamellar structure, which can encapsulate hydrophobic/hydrophilic therapeutic agents. Polymeric nanoparticles, usually applied as micelles, are colloidal carriers composed of biodegradable polymers. Characteristics such as loading capacity, drug release rate, physical and chemical stability, and vesicle size are highly dependent on experimental conditions, and material and method choices at the time of preparation. To be able to develop effective methods for large scale production and to meet the regulatory requirements for eventual clinical implementation of nanocarriers, one needs to have in-depth knowledge of the principles of nanoparticle preparation. This review paper presents an overview of different preparation methods of polymeric and novel lipid-based (niosome and solid lipid) nanoparticles.     

Colorimetric detection of vesicle rupture by attack of Ag nanoparticles

Generally, the cytotoxicity effects of nanomaterials on bio-organisms have been examined using live cells or mice by in-vivo or in-vitro testing. These methodologies, however, are time-consuming, and cell-membrane responses for cytotoxicity are often slow. Therefore, in this study, we proposed a simple testing method for colorimetric detection of dye-containing vesicles as biomimetic cell-membranes. When dye-containing vesicles are ruptured by attack of AgNPs (silver nanoparticles), dye in vesicles is released into the solution, and then the color of solution changes to that of dye. Because the ruptured vesicle causes an optical variation, we could easily and quickly monitor the vesicle rupture by AgNPs. And further, SPR (surface plasmon resonance spectroscopy) and TEM (transmission electron microscopy) analysis were carried out to confirm the vesicle rupturing. It will be provide indirect information for cytotoxicity of nanoparticles.     

气液传质和反应可视化的激光诱导荧光技术

提出了一种先进的可视化测量气液传质和反应的激光诱导荧光技术,其基本原理为利用气相中的臭氧氧化液相中的荧光物质,使用相机定量地捕捉液相中荧光物质（如罗丹明B）发出的荧光信号强度的动态变化,从而记录了气液的传质和反应过程。实验结果通过液相浓度场信息展示了液滴内部丰富的微观混合行为,尤其传递和反应行为敏感于液滴周围环境条件,如微小扰动的均匀流场、扰动强化的非均匀流场和液滴尺寸动态生长过程。直观的可视化测量方法提高了对气液传质和液滴内微观混合行为机理的理解。     

Efficient Encapsulation of a Water-Soluble Molecule into Lipid Vesicles Using W/O/W Multiple Emulsions via Solvent Evaporation

We developed a novel method for preparing lipid vesicles with high entrapment efficiency and controlled size using water‐in‐oil‐in‐water (W/O/W) multiple emulsions as vesicle templates. Preparation consists of three steps. First, a water‐in‐oil (W/O) emulsion containing to‐be‐entrapped hydrophilic molecules in the water phase and vesicle‐forming lipids in the oil phase was formulated by sonication. Second, this W/O emulsion was introduced into a microchannel emulsification device to prepare a W/O/W multiple emulsion. In this step, sodium caseinate was used as the external emulsifier. Finally, organic solvent in the oil phase was removed by simple evaporation under ambient conditions to afford lipid vesicles. The diameter of the prepared vesicles reflected the water droplet size of the primary W/O emulsions, indicating that vesicle size could be controlled by the primary W/O emulsification process. Furthermore, high entrapment yields for hydrophilic molecules (exceeding 80 % for calcein) were obtained. The resulting vesicles had a multilamellar vesicular structure, as confirmed by transmission electron microscopy.     

A study of some intermolecular interactions between organic dye molecules in aqueous solution by fluorescence quenching and difference absorption spectrophotoinetry

Intermolecular interactions between the fluorescent organic dyes Fluorescein, Fluorescein Diiodide, Eosin, Rose Bengal, Erythrosin, Phloxine, Phloxine B, Rhodamine 6G, Lissamine Rhodamine B200 and the non fluorescent Crystal Violet and Malachite Green in aqueous solution have been studied by fluorescence quenching and difference absorption spectrophotometry. Equilibrium constants for the interactions have been determined by the two techniques mentioned and are compared. Absorption and fluorescence spectra and rates of photolysis of solutions obtained by extracting aqueous solutions of the mixed dyes into organic solvents are described.     

Fabrication of CaCO3-Coated Vesicles by Biomineralization and Their Application as Carriers of Drug Delivery Systems

We fabricated CaCO₃-coated vesicles as drug carriers that release their cargo under a weakly acidic condition. We designed and synthesized a peptide lipid containing the Val-His-Val-Glu-Val-Ser sequence as the hydrophilic part, and with two palmitoyl groups at the N-terminal as the anchor groups of the lipid bilayer membrane. Vesicles embedded with the peptide lipids were prepared. The CaCO₃ coating of the vesicle surface was performed by the mineralization induced by the embedded peptide lipid. The peptide lipid produced the mineral source, CO₃²⁻, for CaCO₃ mineralization through the hydrolysis of urea. We investigated the structure of the obtained CaCO₃-coated vesicles using transmission electron microscopy (TEM). The vesicles retained the spherical shapes, even in vacuo. Furthermore, the vesicles had inner spaces that acted as the drug cargo, as observed by the TEM tomographic analysis. The thickness of the CaCO₃ shell was estimated as ca. 20 nm. CaCO₃-coated vesicles containing hydrophobic or hydrophilic drugs were prepared, and the drug release properties were examined under various pH conditions. The mineralized CaCO₃ shell of the vesicle surface was dissolved under a weakly acidic condition, pH 6.0, such as in the neighborhood of cancer tissues. The degradation of the CaCO₃ shell induced an effective release of the drugs. Such behavior suggests potential of the CaCO₃-coated vesicles as carriers for cancer therapies.     

Self-Assembled Structures of Catanionic Associations: How to Optimize Vesicle Formation?

Like other amphiphilic compounds, bolaforms do not always possess surfactant properties; it depends on the spacer chain length and the nature of the polar head group (both sufficiently hydrophobic or hydrophilic, respectively, to intensify the amphiphilic properties). In this regard, unsymmetrical bolaamphiphiles bearing a sugar polar head group and a carboxylic acid function at the opposite ends of a hydrophobic binding spacer were synthesized. These biocompatible sugar-derived bolaforms were associated with basic fatty amines, by an acid–base reaction, to obtain catanionic mixtures. Associations with 1,7-lactobionamidoheptanoic acid and decylamine or octylamine spontaneously form stable 200–600 nm vesicles. This new type of association may find an application in drug delivery since catanionic vesicles can transport active substances inside the hydrophilic core, as well as hydrophobic drugs within the bilayer.     

Effect of Sonication on the Thermotropic Behavior of DODAB Vesicles Studied by Fluorescence Probe Solubilization

The effect of sonication on fluorescence probe solubilization in cationic vesicles of dioctadecyldimethylammonium bromide (DODAB) was investigated by steady-state fluorescence of pyrene (Py), trans-diphenylpolyenes—diphenylbutadiene (DPB), diphenylhexatriene (DPH), and their corresponding 4,4′-dialkyl derivatives 4B4A and 4H4A fluorescence probes. The data indicate that sonication affects the bilayer polarity, the melting temperature (T _m), and the cooperativity of the melting process due to changes in vesicle morphology. The effect of temperature on the fluorescence intensity and yielding Φ_f and anisotropy <r> shows that the ionizable probes 4B4A and 4H4A are solubilized close to the vesicle interfaces, whereas the non-ionizable DPH and DPB are deeper in the bilayers. Py solubilization indicates that sonicated vesicles exhibit less densely packed bilayers.     

Cu~(2+)配位诱导十一胺形成囊泡

文章使用二价金属离子Cu2+以配位作用诱导十一胺形成囊泡相,对囊泡相结构用动态光散射和透射电镜进行了表征,并利用透射电子显微镜(TEM)确认了囊泡的存在,同时对囊包的形成机理进行了探讨和研究。实验发现该囊泡相的形成是由于Cu2+的金属配位作用所导致的。     

Surface plasmon resonance study of (positive, neutral, negative) vesicles rupture by AgNPs’ attack for screening of cytotoxicity induced by nanoparticles

As the use of nanomaterials in industrial and commercial applications is growing, official reports concerning possible environmental and health effects of nanoparticles are also steadily increasing. Many toxicological studies on the adverse effects of silver nanoparticles (AgNPs) have used living organisms, which is a time consuming process. Therefore, we propose an alternative method to assess the in-vivo and in-vitro cytotoxicity of nanomaterials, involving a fast and simple screening procedure for vesicle rupture or fusion by the attack of AgNPs. With the assumption that particle interaction between AgNPs and vesicles is induced by electrostatic repulsion or attraction of surface charge, three vesicles with different charges (positive, neutral, and negative) were prepared and they were dispersed with AgNPs in different pH (3, 7, and 10) solutions to control the surface charge of AgNPs. Based on the results of vesicle rupture analyzed by SPR and TEM, screening of cell rupture through vesicles by AgNPs’ attack is determined to be most suitable at pH 7.     

Novel (Phenothiazinyl)Vinyl-Pyridinium Dyes and Their Potential Applications as Cellular Staining Agents

We report here the synthesis and structural characterization of novel cationic (phenothiazinyl)vinyl-pyridinium (PVP) dyes, together with optical (absorption/emission) properties and their potential applicability as fluorescent labels. Convective heating, ultrasound irradiation and mechanochemical synthesis were considered as alternative synthetic methodologies proficient for overcoming drawbacks such as long reaction time, nonsatisfactory yields or solvent requirements in the synthesis of novel dye (E)-1-(3-chloropropyl)-4-(2-(10-methyl-10H-phenothiazin-3-yl)vinyl)pyridin-1-ium bromide 3d and its N-alkyl-2-methylpyridinium precursor 1c. The trans geometry of the newly synthesized (E)-4-(2-(7-bromo-10-ethyl-10H-phenothiazin-3-yl)vinyl)-1-methylpyridin-1-ium iodide 3b and (E)-1-methyl-4-(2-(10-methyl-10H-phenothiazin-3-yl)vinyl)pyridin-1-ium tetrafluoroborate 3a′ was confirmed by single crystal X-ray diffraction. A negative solvatochromism of the dyes in polar solvents was highlighted by UV-Vis spectroscopy and explanatory insights were supported by molecular modeling which suggested a better stabilization of the lowest unoccupied molecular orbitals (LUMO). The photostability of the dye 3b was investigated by irradiation at 365 nm in different solvents, while the steady-state and time-resolved fluorescence properties of dye 3b and 3a′ in solid state were evaluated under one-photon excitation at 485 nm. The in vitro cytotoxicity of the new PVP dyes on B16-F10 melanoma cells was evaluated by WST-1 assay, while their intracellular localization was assessed by epi-fluorescence conventional microscopy imaging as well as one- and two-photon excited confocal fluorescence lifetime imaging microscopy (FLIM). PVP dyes displayed low cytotoxicity, good internalization inside melanoma cells and intense fluorescence emission inside the B16-F10 murine melanoma cells, making them suitable staining agents for imaging applications.     

A spectroscopic study of the self-association and inter-molecular aggregation behaviour of pH-responsive poly(l-lysine iso-phthalamide)

The pH mediated intra-molecular association and inter-molecular aggregation of a range of amphiphilic poly(l-lysine iso-phthalamide) polymers have been investigated in aqueous solution over a range of pH values and concentrations. The desired functionality of these novel bioresponsive amphiphilic polymers was achieved by incorporating pendant hydrophilic carboxyl groups along the polymer backbone, via the l-lysine moiety, balanced by a degree of hydrophobicity introduced via the iso-phthaloyl moiety. Incorporation of low levels of bis-functional Cy3 (poly-Cy3) and/or Cy5 dye (poly-Cy3/5 or poly-Cy5) co-monomers in the responsive polymer backbone allowed detailed probing of the pH mediated hydrophobic association using a combination of optical spectroscopic techniques. Both steady-state fluorescence spectroscopy and fluorescence lifetime measurements of poly-Cy3 revealed a conformational transition at pH 4.5. Thus, below a critical pH the polymer collapsed into a compact globular structure (hypercoil) bringing the fluorophore molecules into close proximity with one another. This resulted in a dramatic reduction in fluorescence intensity and fluorescent lifetime in the single fluorophore systems (poly-Cy3) accompanied by a red shift in the maximum emission wavelength. Observed redshifts in the emission maxima and enhancements of fluorescent lifetimes with increasing polymer concentration suggested the formation of polymer aggregates. Fluorescence resonance energy transfer (FRET) was measured in mixtures of single fluorophore containing poly-Cy3 (donor) and poly-Cy5 (acceptor) and dual fluorophore containing poly-Cy3 (donor)/Cy5 (acceptor) in an effort to distinguish between intra-molecular versus inter-molecular association. The relevance of the results with respect to potential in vivo applications (drug delivery and biodiagnostics) is discussed.     

Removal of Rhodamine B from aqueous solutions and wastewater by walnut shells: kinetics,equilibrium and thermodynamics studies

An adsorption study of Rhodamine B (RB) dye from aqueous solutions was carried out using walnut shells pretreated by different methods. In addition to the effects of the pretreatment, the effects of various parameters like pH, adsorbent dose, contact time, initial dye concentration and temperature on the adsorption of RB was studied. The adsorption process was highly pH dependent and a maximum adsorption was achieved at pH 3.0. The best fit for the rates of dye adsorption was a pseudo-second-order kinetic model with good correlation coefficients (R²>0.99). Langmuir isotherms were used to determine that the maximum loading capacity of the different walnut shells and the RB capacities ranged from 1.451–2.292 mg·g^-1. The dye adsorption was also evaluated thermodynamically. Positive standard enthalpy (?H°) values were obtained indicating that the RB adsorption process is endothermic as well as ?G° and ?S° values showed that adsorption process is spontaneous with an increased randomness at the solid-liquid interface. Desorption studies were carried out to explore the feasibility of regenerating the used walnut shells and it was found that 97.71%–99.17% of the retained RB was recovered with 0.1 mol?L^-1 NaOH solution. The walnut shells were also successfully used to remove RB from industrial effluents.     

Characterization of electrosterically stabilized polystyrene latex; implications for radical entry kinetics

Electrosterically stabilized polystyrene latexes with a poly(acrylic acid) hydrophilic layer with either perdeuterated core or perdeuterated hydrophilic layer were prepared in situ in a styrene/acrylic acid copolymerization, in a manner similar to that commonly employed industrially. Small angle neutron scattering (SANS) measurements were made over a range of contrasts for three latexes at high and low pH. Parameters obtained by fitting to standard core/shell models were consistent with the shell being highly hydrated (about 89% at low pH and about 94% at high pH). The core was found to contain about 3% acrylic acid. Doubling the proportion of acrylic acid in the recipe increased shell thickness by about 20%, slightly reduced particle size and slightly increased the proportion of acrylic acid incorporated into the core. The maximum degree of polymerization (DOP) of the entering (and therefore grafted) species was estimated from the shell thickness to be about 44 monomer units for 0.02 M acrylic acid and 66 for 0.04 M. The observed dependence of hairy layer (shell) thickness on the initial amount of acrylic acid suggests that the critical DOP for entry (and therefore true grafting) of the electrosteric stabilizer is thermodynamically (not kinetically) controlled.     

Synthesis and evaluation of NiO@MCM-41 core–shell nanocomposite in the CO<Subscript>2</Subscript> reforming of methane

In this paper, the synthesis of core shell structured NiO@MCM-41 nanocomposite via vesicles as soft template is reported for the first time. Its catalytic performance was investigated in the CO₂ reforming of methane (CRM) conversion. Stable vesicles first formed with CTAB/SDBS surfactant ratio of 1:2. Nickle nitrate was added to the vesicle mixture followed by addition of the aqueous solution of vesicle containing Ni cations inside to the MCM-41 gel. After high-temperature calcination, NiO@MCM-41 nanocomposite were obtained. The structural symmetry and the surface morphology were characterized by transmission electron microscope (TEM), low angle X-Ray Diffraction (XRD) and N₂ adsorption/desorption analysis. TEM image confirmed core–shell structure and the hexagonally ordered structure of shell of MCM-41 silica. The results indicated that the average diameter of synthesized core–shell NiO@MCM-41 particles is 70–80 nm and the most of them are of spherical shape. The result of small angle XRD and N₂ isotherm adsorption/desorption analyses indicated successfull formation of mesoporous shell. Hydrogen consumption by the catalyst mainly at 700 °C in TPR profile showed the strong interaction of the most of Nickel content with the support. CRM conversion on the prepared catalyst after 245 min of reaction led to H₂ conversion at 42%, CO₂ conversion at 48% with H₂/CO yield ratio of 0.8.