Unique thermal behavior of acrylic PSAs bearing long alkyl side groups and crosslinked by aluminum chelate

An acrylic pressure-sensitive adhesive (PSA), bearing octadecyl acrylate, methyl acrylate and acrylic acid groups, and crosslinked by aluminum acetylacetonate (AlACA), displayed behavior unique among acrylic PSAs in that its adhesion, which decreases with an increase in temperature, began to increase again from around 150 °C. In order to understand this behavior, the structure and thermal properties of the PSA were investigated in detail, along with another PSA crosslinked by a covalent crosslinking agent (Az). From thermal mechanical analysis, the PSA with ionic crosslinks (AlACA) showed three softening points at 20, 60, and 160 °C. In comparison, the PSA covalently crosslinked by Az only exhibited two softening points (at 20 and 60 °C). The softening point at 160 °C is clearly related to ionic chelate crosslinking. DSC measurements indicated that the softening point at 20 °C resulted from melting of the ordered octadecyl group, and the softening point at 60 °C was due to an increase in the mobility of the main chain. The temperature dependence of viscoelastic measurements revealed that the viscosity of the PSA crosslinked by AlACA increased at around 160 °C. From these results, we considered that the distinctive adhesion of the PSA crosslinked by AlACA could be due to ligand exchange at the aluminum crosslinking points, which are chelated by carboxy groups built in the main chain.     

Siladenoserinols M–P,sulfonated serinol derivatives from a tunicate

Four new sulfonated serinol derivatives, siladenoserinols M–P (1–4), were isolated from a tunicate of the family Didemnidae collected in Indonesia. Their chemical structures were elucidated by the interpretation of NMR and mass spectroscopic data. Two of them (2 and 4) were revealed to be disulfonate serinol derivatives, and the others were monosulfonates. Siladenoserinols A (5) and B (6), which we previously isolated from the same tunicate, inhibited the p53–Hdm2 interaction with an IC₅₀ value of 2.0?μM. However, 1–4 did not inhibit the activity. The result suggested that the acetyl group in the bicyclic ketal unit and/or the glycerophospholipid moiety in 5 and 6 were responsible for the inhibition of the p53–Hdm2 interaction.     

Improvement of Targeted Gene Delivery to Human Cancer Cells by a Novel Trifunctional Crosslinker

A facile method for the construction of an immunoconjugate which displays targeting ligands, such as antibody fragments, with a high density is reported. For this purpose, we synthesized a novel trifunctional crosslinking reagent. By the use of this reagent, ligands targeting the specific cell can be displayed on the surface of the drug carrier with a high density. In this study, we display HER2 (human epidermal growth‐factor receptor‐2) binding ligands on branched polyethylenimine (PEI), which can form polyplexes with plasmid DNA. Kinetic analysis of the binding to the extracellular domain of HER2 show the PEI displaying a high density of ligands binds to the target more strongly compared to the PEI displaying ligands at a low density. The increased density of HER2 ligands displayed on the gene carrier contributes to the improved transfection efficiency. This approach can be applied to other drug delivery systems, including liposome, micelle, and so on.     

Vector model analysis in nondestructive imaging by using the photothermal deflection methods

The noncontact imaging of the buried structures is carried out in the open-air atmosphere by using the photothermal deflection (PTD) method. We applied these techniques to the layered samples. Besides the PTD images for the optically opaque buried structures, the parameters of the materials such as thermal diffusivity can also be calculated from the PTD amplitude and phase signal in the PTD scanning images. When the PTD signals at two different modulation frequencies are used, the thermal diffusivity of the buried structure can be obtained from the PTD signal outside of the sample nondestructively. Received: 27 November 1998 / Accepted: 18 March 1999 / Published online: 7 July 1999     

A function space model approach to the rational evaluation subgroups

Let f : U → X be a map from a connected nilpotent space U to a connected rational space X. The evaluation subgroup G _*(U, X; f), which is a generalization of the Gottlieb group of X, is investigated. The key device for the study is an explicit Sullivan model for the connected component containing f of the function space of maps from U to X, which is derived from the general theory of such a model due to Brown and Szczarba (Trans Am Math Soc 349, 4931–4951, 1997). In particular, we show that non Gottlieb elements are detected by analyzing a Sullivan model for the map f and by looking at non-triviality of higher order Whitehead products in the homotopy group of X. The Gottlieb triviality of a fibration in the sense of Lupton and Smith (The evaluation subgroup of a fibre inclusion, 2006) is also discussed from the function space model point of view. Moreover, we proceed to consideration of the evaluation subgroup of the fundamental group of a nilpotent space. In consequence, the first Gottlieb group of the total space of each S ¹-bundle over the n-dimensional torus is determined explicitly in the non-rational case.