声子色散和磁场对极性晶体中极化子自陷能的影响

利用线性组合算符和幺正变换相结合的方法,研究了声子色散和磁场对极性晶体中极化子振动频率和自陷能的影响.计及纵光学(LO)声子色散,在抛物近似下导出了极性晶体中极化子自陷能随电子-纵光学声子耦合常数、回旋共振频率和声子色散系数之间的变化关系.数值计算结果表明极化子自陷能随电子-纵光学声子耦合常数、回旋共振频率和声子色散系数的增大而增大.     

The development and assessment of high‐throughput mass spectrometry‐based methods for the quantification of a nanoparticle drug delivery agent in cellular lysate

The safe use of lipid‐based drug delivery agents requires fast and sensitive qualitative and quantitative assessment of their cellular interactions. Many mass spectrometry (MS) based analytical platforms can achieve such task with varying capabilities. Therefore, four novel high‐throughput MS‐based quantitative methods were evaluated for the analysis of a small organic gene delivery agent: N,N‐bis(dimethylhexadecyl)‐1,3‐propane‐diammonium dibromide (G16‐3). Analysis utilized MS instruments that detect analytes using low‐resolution tandem MS (MS/MS) analysis (i.e. QTRAP or linear ion trap in this work) or high‐resolution MS analysis (i.e. time of flight (ToF) or Orbitrap). Our results indicate that the validated fast chromatography (FC)‐QTRAP‐MS/MS, FC‐ LTQ‐Orbitrap‐MS, desorption electrospray ionization‐collision‐induced dissociation (CID)‐MS/MS and matrix assisted laser desorption ionization‐ToF/ToF‐MS MS methods were superior in the area of method development and sample analysis time to a previously developed liquid chromatography (LC)‐CID‐MS/MS. To our knowledge, this is the first evaluation of the abilities of five MS‐based quantitative methods that target a single pharmaceutical analyte. Our findings indicate that, in comparison to conventional LC‐CID‐MS/MS, the new MS‐based methods resulted in a (1) substantial reduction in the analysis time, (2) reduction in the time required for method development and (3) production of either superior or comparable quantitative data. The four new high‐throughput MS methods, therefore, were faster, more efficient and less expensive than a conventional LC‐CID‐MS/MS for the quantification of the G16‐3 analyte within tissue culture. When applied to cellular lysate, no significant change in the concentration of G16‐3 gemini surfactant within PAM212 cells was observed between 5 and 53 h, suggesting the absence of any metabolism/excretion from PAM212 cells. Copyright © 2014 John Wiley & Sons, Ltd.     

Effect of reactive and non-reactive counterion micelles upon the alkaline degradation of indomethacin

In the present paper, kinetics of alkaline degradation of well known drug, indomethacin (2-[1-(4-chlorobenzoyl)-5-methoxy-2-methylindol-3-yl]acetic acid), was studied in presence of excess [NaOH]. The rate of hydrolysis of substrate was independent of the [indomethacin] though it increased linearly with increasing the hydroxide ion concentration with a positive slope, suggesting the following rate law: k_obs = k₁[OH⁻]. Cationic surfactants having non-reactive ions (cetyltrimethylammonium bromide, CTAB and cetyltrimethylammonium sulfate (CTA)₂SO₄) first increased the rate constants at lower concentrations and then decreased it at higher concentrations while in case of the surfactant with reactive counterions (cetyltrimethylammonium hydroxide, CTAOH) the rate increases sharply at lower concentrations of surfactant until it reaches to a plateau in contrast to the appearance of maxima in case of CTAB and (CTA)₂SO₄. Anionic surfactant, sodium dodecyl sulfate (SDS), inhibited the reaction rate at all concentrations used in the study. Pseudophase ion-exchange model was used for analyzing the effect of cationic micelles while the inhibition by SDS micelles was fitted using the Menger–Portnoy model. The effect of salts (NaCl, NaBr and (CH₃)₄NBr) was also seen on the hydrolysis of indomethacin and it was found that all salts inhibited the rate of reaction. The inhibition followed the trend NaCl < NaBr < (CH₃)₄NBr.     

Peptide Nanotubes

The self‐assembly of different classes of peptide, including cyclic peptides, amyloid peptides and surfactant‐like peptides into nanotube structures is reviewed. The modes of self‐assembly are discussed. Additionally, applications in bionanotechnology and synthetic materials science are summarized.     

Channelled Porous TiO2 Synthesized with a Water‐in‐Oil Microemulsion

Porous titanium dioxide synthesized with a bicontinuous surfactant template is a promising method that leads to a high active surface area electrode. The template used is based on a water/isooctane/dioctyl sodium sulfosuccinate salt together with lecithin. Several parameters were varied during the synthesis to understand and optimize channel formation mechanisms. The material is patterned in stacked conical channels, widening towards the centre of the grains. The active surface area increased by 116 % when the concentration of alkoxide precursors was decreased and increased by 241 % when the template formation temperature was decreased to 10 °C. Increasing the oil phase viscosity tends to widen the pore aperture, thus decreasing the overall active surface area. Changing the phase proportions alters the microemulsion integrity and disrupts channel formation.     

A Selective Release System Based on Dual‐Drug‐Loaded Mesoporous Silica for Nanoparticle‐Assisted Combination Therapy

A selective release system was demonstrated with a dual‐cargo loaded MSNs. When stimulated by different signals (UV or H⁺), this system could selectively release different kinds of cargoes individually. Furthermore, this system has been used to provide a combination of chemotherapy and biotherapy for cancer treatment. This controlled release system could be an important step in the development of more effective and sophisticated nanomedicine and nanodevices, due to the possibility of selective release of a complex multi‐drug.     

Asymmetric Gold‐Catalyzed Lactonizations in Water at Room Temperature

Asymmetric gold‐catalyzed hydrocarboxylations are reported that show broad substrate scope. The hydrophobic effect associated with in situ‐formed aqueous nanomicelles gives good to excellent ee’s of product lactones. In‐flask product isolation, along with the recycling of the catalyst and the reaction medium, are combined to arrive at an especially environmentally friendly process.     

Monitoring the Transition from Spherical to Polymer‐like Surfactant Micelles Using Small‐Angle X‐Ray Scattering

Despite over a century of modern surfactant science, the kinetic pathways of morphological transitions in micellar systems are still not well understood. This is mainly as a result of the lack of sufficiently fast methods that can capture the structural changes of such transitions. Herein, a simple surfactant system consisting of sodium dodecyl sulfate (SDS) in aqueous NaCl solutions is investigated. Combining synchrotron radiation small‐angle X‐ray scattering (SAXS) with fast stopped‐flow mixing schemes allows monitoring the process where polymer‐like micelles are formed from globular micelles when the salt concentration is suddenly increased. The results show that “worm‐like” micelles are formed by fusion of globular micelles and short cylinders in a fashion that bears similarities to a step‐like polymerization process.     

Tailoring of High‐Order Multiple Emulsions by the Liquid–Liquid Phase Separation of Ternary Mixtures

Multiple emulsions with an “onion” topology are useful vehicles for drug delivery, biochemical assays, and templating materials. They can be assembled by ternary liquid phase separation by microfluidics, but the control over their design is limited because the mechanism for their creation is unknown. Herein we show that phase separation occurs through self‐similar cycles of mass transfer, spinodal decomposition or nucleation, and coalescence into multiple layers. Mapping out the phase diagram shows a linear relationship between the diameters of concentric layers, the slope of which depends on the initial ternary composition and the molecular weight of the surfactant. These general rules quantitatively predict the number of droplet layers (multiplicity), which we used to devise self‐assembly routes for polymer capsules and liposomes. Moreover, we extended the technique to the assembly of lipid‐stabilized droplets with ordered internal structures.     

Effect of Protic Ionic Liquid and Surfactant Structure on Partitioning of Polyoxyethylene Non‐ionic Surfactants

The partitioning constants and Gibbs free energies of transfer of poly(oxyethylene) n‐alkyl ethers between dodecane and the protic ionic liquids (ILs) ethylammonium nitrate (EAN) and propylammonium nitrate (PAN) are determined. EAN and PAN have a sponge‐like nanostructure that consists of interpenetrating charged and apolar domains. This study reveals that the ILs solvate the hydrophobic and hydrophilic parts of the amphiphiles differently. The ethoxy groups are dissolved in the polar region of both ILs by means of hydrogen bonds. The environment is remarkably water‐like and, as in water, the solubility of the ethoxy groups in EAN decreases on warming, which underscores the critical role of the IL hydrogen‐bond network for solubility. In contrast, amphiphile alkyl chains are not preferentially solvated by the charged or uncharged regions of the ILs. Rather, they experience an average IL composition and, as a result, partitioning from dodecane into the IL increases as the cation alkyl chain is lengthened from ethyl to propyl, because the IL apolar volume fraction increases. Together, these results show that surfactant dissolution in ILs is related to structural compatibility between the head or tail group and the IL nanostructure. Thus, these partitioning studies reveal parameters for the effective molecular design of surfactants in ILs.