Cerasome as an Organic-Inorganic Vesicular Nanohybrid: Characterization of Cerasome-Forming Lipids having a Single or a Dual Trialkoxysilyl Head

Morphological characterization of the organic-inorganic vesicular nanohybrids, Cerasomes, was performed in aqueous media from two aspects. Firstly, a novel Cerasome-forming lipid having two triethoxysilyl groups in the head moiety was synthesized and the physical property of the Cerasome was investigated. While the morphological stability of the Cerasomes, as evaluated from the vesicular collapse behavior against a micelle-forming nonionic surfactant, Triton-X 100, was extremely higher than that of the conventional phospholipid liposome, the stabilities were comparable to each other for the Cerasomes derived from the dual- and single-head lipids. On the other hand, the surface property of the Cerasome formed with the dual-head lipid more closely resembled the colloidal silica particles rather than that derived from the single-head lipid, as suggested by zeta-potential measurements. Secondly, the effect of the media pH on the morphological stability of the Cerasome formed with the single-head lipid was evaluated and appeared as a time difference in obtaining the morphological stability of the Cerasome. These morphological characteristics of the Cerasomes could be mainly owing to the development of the siloxane network on the vesicular surface.     

Incorporation of lipid domains in Cerasome, a morphologically-stable organic-inorganic vesicular nanohybrid

To extend the concept of the Cerasome, an organic-inorganic vesicular nanohybrid, this paper investigates the preparation and characterization of a “mixed” Cerasome. The system consists of a Cerasome-forming lipid 1, a cationic synthetic lipid 2, and a zwitterionic phospholipid 3. Lipid mixtures of 1 and 2 or 1 and 3 were used to prepare the mixed Cerasomes. Their lipid distributions were examined using differential scanning calorimetry (DSC), which showed that 1 and 2 (or 1 and 3) were phase-separated in the mixed Cerasomes. These results seem to be mainly attributable to the polymerizable nature of 1. Results of scanning electron microscopy (SEM) and energy-dispersive X-ray analysis (EDX) showed that 1 and 3 were both incorporated into a single Cerasome, not macroscopically separated to form separate vesicles from each lipid component. Mixed Cerasomes of 1 and 2 showed high morphological stability against a membrane-solubilizing surfactant, incorporating up to 70% of 2. On the other hand, the mixed Cerasomes from 1 and 3 were less stable than the mixed Cerasomes from 1 and 2. This relative instability might be attributable to differences between the mixed Cerasomes from 1 and 2 and 1 and 3 in terms of their vesicular sizes, lipid domain sizes, and their relative effectiveness for siloxane network formation. These results strongly support the formation of mixed Cerasomes that have lipid domains in-plane. Systems described in this study are useful to prepare variously mixed Cerasomes that have different surface functionalities and in-plane lipid distribution, but which have high morphological stability.     

Uncharged water-soluble Co(II)-porphyrin: a receptor for aromatic alpha-amino acids

Changes in the UV-vis spectra and induced circular dichroism (ICD) signals observed, in correspondence with the porphyrin Soret region, for aqueous solutions of achiral 5,10,15,20-tetrakis{p-[omega-methoxy poly(oxy-ethylene)]phenyl}porphyrin cobalt (II) (Co-P) and aromatic alpha-L-amino acids (Trp and Phe) give direct evidence for the coordination between the Co-P and amino acids. Considering that Co-P, besides the Co atom (one-fixation-point system), does not contain in the molecule active ligand groups and that no ICD signals have been observed in the case of Co-P/Ala, it has been concluded that hydrophobic interactions or stacking interactions between the aromatic rings of the porphyrin and those of Trp or Phe, acting as further amino acid (AA) fixation points, can strongly reduce the mobility of the chiral guest, thus permitting the generation of ICD signals. The effects of changes of both pH (in the range 2-9) and amino acid structure on the ICD phenomenon have also been investigated. In particular, the following have been observed: (i) strong ICD signals for all of the Co-P/N-acetyl amino acid aqueous solutions at pH 7, (ii) an unexpected ICD band with a bisignate form for the Co-P/Ala solution at pH 9 after long aging, and (iii) an opposite ICD signal when alpha-D-Phe and alpha-D-Trp enantiomers have been used. The data reported in this paper show how the binding mechanism between receptor and AAs changes by modulating properly the pH or the molecular structures and indicate that in these aqueous solutions the coordination Co-N is not the fundamental mechanism giving rise to the formation of the complexes and that the binding can be driven by hydrophobic interactions. These occurrences, through the analysis of the spectroscopic response (and, in particular, the form of the ICD band), can allow the recognition of AAs.     

Effect of delay time and grid voltage changes on the average molecular mass of polydisperse polymers and polymeric blends determined by delayed extraction matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

The dependence of the calculated average molecular mass of a polyethylene glycol with a large polydispersity on the instrumental parameters adopted in the acquisition of mass spectra using delayed extraction matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (DE MALDI-TOFMS) was investigated. It has been shown that a combined effect of delay times and potential gradients can act on the ion cloud in the source chamber affecting both mass resolution and average molecular mass value of the analyzed polymeric sample. Also examined was a blend of two different polymers (a PEG and a PMMA commercial sample having a similar average molecular mass), which presents an additional problem concerning the discrimination among the different polymer species as a function of the experimental conditions. In this work, the best instrumental conditions to obtain both good resolution and a correct average molecular mass for the examined polydisperse sample are reported.     

Positron binding energies for alkali hydrides

Ab initio multireference single- and double-excitation configuration interaction (MRD-CI) calculations are carried out to study the interactions of positrons with the members of the alkali hydride class of molecules. A new computer program has been constructed for this purpose that makes use of the Table-Direct-CI method for construction of the required Hamiltonian matrixes and electronic/positronic wave functions. The calculations indicate that the binding energy (positron affinity PA) of a single positron to these systems increases by an increment of 0.2-0.3 eV as the atomic number of the alkali atom is increased. It is found that the positron prefers a location in the more electronegative regions of such molecules, similarly as has been found in earlier calculations for the urea and acetone molecules. The positron orbital itself possesses a diffuse charge distribution with relatively small expectation values of the kinetic energy in all four systems considered. Each of the four positronic molecules is stable with respect to formation of either positronium (Ps) or HPs according to the present calculations. Relatively large changes in the equilibrium bond distance of the hydrides occur as a result of the positron interaction. The importance of bond dipole moments in producing the binding of positrons to molecules is discussed, as well as the role that the electronegativity of the constituent atoms plays in determining the magnitude of the PA for a given system.     

Test compounds for detecting the silanol effect on the elution of ionized amines in reversed‐phase LC

The effectiveness of several basic compounds for testing silica‐based stationary phases was reviewed by applying them to recent columns for reversed‐phase HPLC. Most octadecylsilylated (C18) stationary phases, prepared as a base‐deactivated material from high‐purity silica gel with endcapping, provided excellent peak shape and column efficiency for the bases including benzylamine and amitriptyline that once caused problems and were subsequently employed for testing silanol activities. However, a cyclic tertiary amine, dextrometorphan, was eluted as an acceptable peak from only a few columns at neutral pH. Such a more sensitive probe is expected to contribute to further improvement of the stationary phase for reversed‐phase HPLC.     

Possible Involvement of a Tetrahydrobiopterin in Photoreception for UV‐B‐induced Anthocyanin Synthesis in Carrot

Our previous studies of action spectra for UV‐B‐induced anthocyanin accumulation in cultured carrot cells indicated that a reduced form of pterin, possibly tetrahydrobiopterin, contributes to UV‐B photoreception. In this report, we provide additional evidence for the involvement of pterin in UV‐B light sensing. UV‐B‐induced phenylalanine ammonia‐lyase (PAL) activity was considerably suppressed by N‐acetylserotonin (an inhibitor of tetrahydrobiopterin biosynthesis), and this suppression was partially recovered by adding biopterin or tetrahydrobiobiopterin. In addition, protein(s) specifically bound to biopterin were detected by radiolabeling experiments in N‐acetylserotonin‐treated cells. Furthermore, diphenyleneiodonium, a potent inhibitor of electron transfer, completely suppressed UV‐B‐induced PAL activity. These results suggest the occurrence of an unidentified UV‐B photoreceptor (other than UVR8, the tryptophan‐based UV‐B sensor originally identified in Arabidopsis) with reduced pterin in carrot cells. After reexamining published action spectra, we suggest that anthocyanin synthesis is coordinately regulated by these two UV‐B sensors.     

Effect of preparative conditions on crystallinity of apatite particles obtained from simulated body fluids

Preparation of colloidal hydroxyapatite (HAp) particles under body fluid conditions was investigated with focusing on the effect of preparative conditions on crystallinity of the resulting particles. Tris(hydroxymethyl)aminomethane was added to 1.5SBF (a solution having 1.5 times higher ion concentrations than those of a simulated body fluid, SBF) to increase the solution pH, which resulted in induction of homogeneous nucleation of HAp in the solution. Colloidal HAp particles having diameters about 300 nm were obtained. When the reaction was proceeded at 70°C and the sample was dried by heating, it was effective to obtain HAp particles having high crystallinity. Experimental results support that remaining water in the sample contributed to increase HAp crystallinity.