Inflammation-induced synergetic enhancement of nanoparticle treatments with DOXIL<Superscript>®</Superscript> and <Superscript>90</Superscript>Y-Lactosome for orthotopic mammary tumor

Polymeric micelles (Lactosome) in the size of 20–30 nm were labeled with radionuclides of ¹¹¹In (¹¹¹In-DOTA-Lactosome) for SPECT imaging and ⁹⁰Y (⁹⁰Y-DOTA-Lactosome) for β-ray irradiation for mammary tumor in mice. The tumor site at the femoral right leg grafted with 4T1 cells was clearly imaged at 24 h after the intravenous injection. Biodistribution revealed that the half-life time of ¹¹¹In-DOTA-Lactosome was 11 h, which enabled the nanoparticle selectively accumulated in tumor site due to the enhanced permeability and retention (EPR) effect. The anti-tumor therapeutic effect of ⁹⁰Y-DOTA-Lactosome was observed depending on the dose frequency and amount. Under the condition of the percutaneous ethanol injection treatment, the therapeutic effect of ⁹⁰Y-DOTA-Lactosome was enhanced due to the super EPR effect. Owing to the super EPR effect, co-administration of ⁹⁰Y-DOTA-Lactosome and DOXIL^® inhibited the tumor growth during 15 days with their administrations.     

Photoinduced electron transfer in thin layers composed of fullerene-cyclic peptide conjugate and pyrene derivative

A bilayer structure was constructed on gold by Langmuir-Blodgett deposition of a fullerene (C 60)-cyclic peptide-poly(ethylene glycol) (PEG) conjugate and thereafter a pyrene derivative from the air/water interface. The cyclic peptide moiety acts as a scaffold to prevent the fullerenes from self-aggregation and accordingly makes the monolayer homogeneous and stable. In addition to this gold/C 60-cyclic peptide-PEG/pyrene bilayer, a pyrene monolayer, a gold/C 60-PEG conjugate/pyrene bilayer (lacking the peptide scaffold), and a gold/pyrene/C 60-cyclic peptide-PEG bilayer (with the opposite order of layers) were also prepared, and their anodic photocurrent generation were studied in an aqueous solution containing a sacrifice electron donor. The most efficient photocurrent generation was observed in the gold/C 60-cyclic peptide-PEG/pyrene bilayer. It is considered that the C 60 unit acts not only as sensitizer but also as an electron acceptor facilitating the electron transfer from the excited pyrene unit to gold, and that the fullerene layer suppresses quenching of the excited pyrene unit by energy transfer to gold. Furthermore, the cyclic peptide scaffold helps the fullerenes disperse without aggregation in the membrane and seems to protect their redox properties or inhibit self-quenching of their excited state. It is thus concluded that a bilayer structure with desired orientation of functional units is important for efficient photoinduced electron transfer and that a cyclic peptide scaffold is useful to locate hydrophobic functional groups properly in a thin layer.     

Vertical and directional insertion of helical peptide into lipid bilayer membrane

A novel helical hexadecapeptide carrying a poly(ethylene glycol) (PEG) chain at the N terminal was synthesized. The N and C terminals of the compound are labeled with a fluorescein isothiocyanate (FITC) group and an N-ethylcarbazolyl group (ECz), respectively. An octapeptide carrying the same groups and a hexadecapeptide without a PEG chain were also synthesized and used as control. A mixture of the peptide and dimyristoylphosphatidylcholine was sonicated in a buffer to prepare the liposome. The orientation as well as direction of the helical segment in the lipid bilayer were analyzed by quenching experiments of the FITC and the ECz fluorescence. The results clearly indicated that the helical segment of the peptide penetrated into the lipid bilayer with vertical orientation in both the gel and liquid crystalline states of the lipid bilayer. Notably, the bulky N terminal was left behind in the outer aqueous phase of liposome, meaning that the C terminal of the peptide points to the inner aqueous phase of liposome. The insertion mode of the helical peptide into a bilayer membrane is therefore well-regulated in terms of the orientation and the directionality by designing the balance between the PEG chain and the helix length. The methodology presented here will initiate a way to construct artificial functional molecular systems that can induce vectorial transport phenomena as seen in biological systems.     

Nanotube and three-way nanotube formation with nonionic amphiphilic block peptides

Amphiphilic block polypeptides having a helical hydrophobic block with a uniform chain length and a hydrophilic nonionic block were newly synthesized and self-assembled into homogeneous nanotubes with ca. 60 nm diameter and ca. 200 nm length. The tubular assembly was shown to be elongated by heating over micrometer length without changing the diameter. Notably, a distinctive three-way nanotube was obtained just by mixing two kinds of amphiphilic polypeptides with the same helical hydrophobic block but different chain lengths of the hydrophilic block. The morphology of the molecular assemblies was shown to be tunable from a curved sheet-shaped assembly to a long or short nanotubular assembly and a three-way nanotubular assembly by suitable molecular design of the hydrophobic block, selection of the chain length of the hydrophilic block, mixing two-type block peptides, and processing such as heating.     

Molecular dipole engineering: new aspects of molecular dipoles in molecular architecture and their functions

The assembly of molecular architectures on the basis of molecular dipoles is proposed here to be a promising tool for construction of nanomaterials and nanodevices. Three kinds of building blocks having dipoles are discussed; helical peptides, cyclic beta-peptides, and oligo(phenylene ethynylene)s having donor and acceptor substituents. Secondary interactions involving molecular dipoles are shown to be effective to control precise molecular shapes and to assemble the building blocks in a regular manner. Furthermore, molecular dipoles can generate a strong electric field at the nanoscale, which is useful for the promotion or suppression of electron transfer processes. Organic molecules with strong dipoles will therefore be applicable to various fields, such as molecular electronics and medical chemistry, as functional nanomaterials. It is expected that the chemistry of dipolar molecules will lay a firm foundation for a new interdisciplinary field, that of "molecular dipole engineering".     

A new reference material for radionuclides in the mussel sample from the Mediterranean Sea (IAEA-437)

A new Reference Material (RM) for radionuclides in mussel (Mytilus galloprovincialis) from the Mediterranean Sea (IAEA-437) is described and the results of the certification process are presented. Four radionuclides (⁴⁰K, ²³⁴U, ²³⁸U, and ^239+240Pu) have been certified, and information values on massic activities with 95% confidence intervals are given for nine radionuclides (¹³⁷Cs, ²¹⁰Pb(²¹⁰Po), ²²⁶Ra, ²²⁸Ra, ²²⁸Th, ²³⁰Th, ²³²Th, ²³⁵U, and ²⁴¹Am). Results for less frequently reported radionuclides (⁹⁰Sr, ¹²⁹I, ²³⁸Pu, ²³⁹Pu, and ²⁴⁰Pu) are also reported. The RM can be used for quality assurance/quality control of the analysis of radionuclides in mussel samples, for the development and validation of analytical methods and for training purposes. The material is available in 200 g units.     

β-Galactosidase fluorescence probe with improved cellular accumulation based on a spirocyclized rhodol scaffold

We identified a rhodol bearing a hydroxymethyl group (HMDER) as a suitable scaffold for designing fluorescence probes for various hydrolases. HMDER shows strong fluorescence at physiological pH, but phenolic O-alkylation of HMDER results in a strong preference for the spirocyclic form, which has weak fluorescence. As a proof of concept, we utilized this finding to develop a new fluorescence probe for β-galactosidase. This probe has favorable characteristics for imaging in biological samples: it has good cellular permeability, and its hydrolysis product is well-retained intracellularly. It could rapidly and clearly visualize β-galactosidase activity in cultured cells and in Drosophila melanogaster tissue, which has rarely been achieved with previously reported fluorescence probes.     

Controllable fabrication and characterization of conical nanocarbon structures on polymer substrate for transparent and flexible field emission displays

The direct fabrication of fully transparent conical nanocarbon structures (CNCSs) of controlled nanoscopic dimension on a flexible nafion substrate was achieved, using field electron source, by a novel room temperature ion irradiation technique. By controlling the sizes (below the wavelength of visible light) of the CNCSs, the transparency of the substrate can be tailored satisfactorily. The transparency of the CNCSs was observed to be around 90% in the visible regime depending on the ion irradiation time. Our results suggest that the direct fabrication of well controlled fully transparent CNCSs on any transparent and flexible substrate at room temperature could open a novel route for potential applications in future highly transparent, flexible (bendable), low weight and portable field emission displays (FEDs). (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Novel liquid crystal multistage circular polarization switch for three-dimensional laser pico projectors

Crosstalk is one of the most important factors affecting the image quality of polarization switching three-dimensional (3D) projectors. The variation in the phase difference of a polarization switch owing to dispersion degrades crosstalk performance. We propose a novel multistage circular polarization switch comprising liquid crystal devices using a ferroelectric liquid crystal (FLC) in-plane fast switch and a thick nematic liquid crystal (NLC) retarder. In this paper, we present a proof-of-concept model of a 3D laser pico projector using a scanning MEMS head in combination with the polarization switch. We also evaluate the crosstalk and 3D performance of the projector.